2-heteroaryl-3,4-dihydro-2h-pyrrole derivatives and the use thereof as pesticides

ABSTRACT

Novel Δ 1 -pyrrolines of the Formula (I) 
                         
in which
     R 1 , R 2 , R 3  and Het have the meanings given in the description,
 
a plurality of processes for preparing these compounds and their use for controlling pests, and also novel intermediates and processes for their preparation.

The present invention relates to novel Δ¹-pyrrolines, to a plurality ofprocesses for their preparation and to their use as pesticides.

It is already known that numerous Δ¹-pyrrolines have insecticidalproperties (cf. WO 00/21958, WO 99/59968, WO 99/59967 and WO 98/22438).The activity of these substances is good; however, in some cases it isunsatisfactory.

This invention now provides Δ¹-pyrrolines of the formula (I),

in which

-   R¹ represents halogen, in each case optionally substituted alkyl,    alkoxy or —S(O)_(w)R⁴,-   R² and R³ independently of one another represent hydrogen, halogen    or in each case optionally substituted alkyl, alkoxy or alkoxyalkyl,-   R⁴ represents optionally substituted alkyl,-   Het represents heteroaryl which is optionally mono- or    polysubstituted by identical or different R⁵,-   R⁵ represents the grouping —X—Y-Z-E with the proviso that Y does not    represent a direct bond if X does not represent a direct bond,-   X represents a direct bond, oxygen, —S(O)_(w)—, —NR⁶—, carbonyl,    carbonyloxy, oxycarbonyl, oxysulphonyl (OSO₂), alkylene,    halogenalkylene, alkenylene, halogenoalkenylene, alkinylene,    alkyleneoxy, oxyalkylene, oxyalkyleneoxy, —S(O)_(w)-alkylene,    cyclopropylene or oxiranylene,-   Y represents a direct bond or represents in each case optionally    substituted phenylene, naphthylene, tetrahydronaphthylene or    heterocyclylene,-   Z represents a direct bond or —(CH₂)_(n)—,-   E represents hydrogen, halogen, hydroxyl, cyano, formyl, nitro,    trialkylsilyl, pentafluorothio, —S(O)_(w)R⁷, —OSO₂R⁷, —NR⁸R⁹, —COR⁷,    —CO₂R⁷, —OC(O)R⁷, —CONR¹⁰R¹¹, —N(R¹²)COR¹³, —C(R¹⁴)═N—OR¹⁵,    —SO₂NR¹⁶R¹⁷; represents in each case optionally substituted alkyl,    alkenyl, alkinyl, alkoxy, alkenyloxy, cycloalkyl, cycloalkylalkyl,    cycloalkyloxy, aryl, arylalkyl, aryloxy, aryloxyalkyl, saturated or    unsaturated heterocyclyl or heterocyclylalkyl,-   R⁶ represents in each case optionally substituted alkyl, cycloalkyl,    cycloalkylalkyl, aryl or arylalkyl,-   R⁷ represents in each case optionally substituted alkyl, cycloalkyl,    aryl or arylalkyl,-   R⁸ and R⁹ independently of one another represent hydrogen, —SO₂R⁷,    —COR⁷, —CO₂R⁷, represent in each case optionally substituted alkyl,    alkenyl, cycloalkyl, cycloalkylalkyl, aryl, arylalkyl or saturated    or unsaturated heterocyclyl or heterocyclylalkyl,-   R⁸ and R⁹ furthermore together represent in each case optionally    substituted alkenylene or alkylene, where the alkylene chain may in    each case be interrupted by —O—, —S— or —NR¹⁸—,-   R¹⁰ and R¹¹ independently of one another represent hydrogen, —SO₂R⁷,    represent in each case optionally substituted alkyl, alkenyl,    cycloalkyl, cycloalkylalkyl; aryl, arylalkyl or saturated or    unsaturated heterocyclyl or heterocyclylalkyl,-   R¹⁰ and R¹¹ furthermore together represent optionally substituted    alkylene, where the alkylene chain may in each case be interrupted    by —O—, —S— or —NR¹⁸—,-   R¹² and R¹³ independently of one another represent hydrogen,    represent in each case optionally substituted alkyl, cycloalkyl,    cycloalkylalkyl, aryl or arylalkyl,-   R¹² and R¹³ furthermore together represent in each case optionally    substituted alkylene or alkenylene,-   R¹⁴ and R¹⁵ independently of one another represent hydrogen,    represent in each case optionally substituted alkyl or alkenyl,-   R¹⁶ and R¹⁷ independently of one another represent hydrogen,    represent optionally substituted alkyl or cycloalkyl,-   R¹⁶ and R¹⁷ furthermore together represent optionally substituted    alkylene, alkoxyalkylene or alkylthioalkylene,-   R¹⁸ represents hydrogen, —SO₂R⁷, —COR⁷ or —CO₂R⁷; represents in each    case optionally substituted alkyl, alkenyl, cycloalkyl,    cycloalkylalkyl, aryl, arylalkyl or saturated or unsaturated    heterocyclyl or heterocyclylalkyl,-   w represents 0, 1 or 2,-   n represents 1, 2, 3 or 4.

Depending on the nature and number of substituents, the compounds of theformula (I) can, if appropriate, be present as geometrical and/oroptical isomers, regioisomers and/or configurational isomers or isomermixtures thereof of varying composition. What is claimed by theinvention are both the pure isomers and the isomer mixtures.

Furthermore, it has been found that the novel compounds of the formula(I) can be obtained by one of the processes described below.

-   Δ¹-Pyrrolines of the formula (I)

in which

-   R¹, R², R³ and Het have the meanings given above    can be prepared by-   A) treating amino ketones of the formula (II)

-   -   in which    -   R¹, R², R³ and Het have the meanings given above    -   with a Lewis acid or a protonic acid, if appropriate in the        presence of a diluent,        or

-   B) reacting azides of the formula (III)

-   -   in which    -   R¹, R², R³ and Het have the meanings given above    -   with a trialkylphosphine or a triarylphosphine or a trialkyl        phosphite or a reducing agent in the presence of a diluent and,        if appropriate, in the presence of a catalyst,        or

-   C) reacting amides of the formula (IV)

-   -   in which    -   R¹⁹ represents alkyl, halogenoalkyl, aryl or arylalkyl and    -   R¹, R², R³ and Het have the meanings given above    -   with an N-deacetylating agent, if appropriate in the presence of        a diluent.

-   Δ¹-Pyrrolines of the formula (I-a)

in which

-   Het¹ represents heteroaryl which is monosubstituted by R⁵⁻¹,-   R⁵⁻¹ represents the grouping —Y¹-E,-   Y¹ represents in each case optionally substituted phenylene or    heterocyclylene,-   R¹, R², R³ and E have the meanings given above    can be prepared by-   D) reacting Δ¹-pyrrolines of the formula (I-b)

-   -   in which    -   Het² represents heteroaryl which is monosubstituted by R⁵⁻²,    -   R⁵⁻² represents chlorine, bromine, iodine, —OSO₂CF₃ or        —OSO₂(CF₂)₃CF₃ and    -   R¹, R² and R³ have the meanings given above    -   with (hetero)cycles of the formula (V)        A¹-Y¹-E  (V)    -   in which    -   Y¹ and E have the meanings given above and    -   A¹ represents chlorine, bromine, iodine, —OSO₂CF₃ or        —OSO₂(CF₂)₃CF₃,    -   in the presence of a catalyst, in the presence of a diboronic        ester and, if appropriate, in the presence of an acid binder        and, if appropriate, in the presence of a diluent, in a tandem        reaction,        or

-   E) reacting Δ¹-pyrrolines of the formula (VI)

-   -   in which    -   Het³ represents heteroaryl which is monosubstituted by A²,    -   A² represents —B(OH)₂,        (4,4,5,5-tetramethyl-1,3,2-dioxaborolan)-2-yl,        (5,5-dimethyl-1,3,2-dioxaborinan)-2-yl,        (4,4,6-trimethyl-1,3,2-dioxaborinan)-2-yl or        1,3,2-benzodioxaborol-2-yl and    -   R¹, R² and R³ have the meanings given above    -   with heterocycles of the formula (V)        A¹-Y¹-E  (V)    -   in which    -   Y¹, E and A¹ have the meanings given above    -   in the presence of a catalyst, if appropriate in the presence of        an acid binder and if appropriate in the presence of a diluent,        or

-   F) reacting Δ¹-pyrrolines of the formula (I-b)

-   -   in which    -   R¹, R², R³ and Het² have the meanings given above    -   with boronic acid derivatives of the formula (VII)        A²-Y¹-E  (II)    -   in which    -   Y¹, E and A² have the meanings given above    -   in the presence of a catalyst, if appropriate in the presence of        an acid binder and if appropriate in the presence of a diluent,        or

-   G) reacting Δ¹-pyrrolines of the formula (I-c)

-   -   in which    -   Het⁴ represents heteroaryl which is monosubstituted by R⁵⁻³,    -   R⁵⁻³ represents bromine or iodine and    -   R¹, R² and R³ have the meanings given above    -   with organometallic compounds of the formula (VIII)        M-Y¹-E  (VIII)    -   in which    -   Y¹ and E have the meanings given above and    -   M represents ZnCl, Sn(Me)₃ or Sn(n-Bu)₃,    -   in the presence of a catalyst, if appropriate in the presence of        an acid binder and if appropriate in the presence of a diluent.

Finally, it has been found that the compounds of the formula (IDaccording to the invention have very good insecticidal properties andcan be used both in crop protection and in the protection of materialsfor controlling, undesirable pests, such as insects.

The formula (I) provides a general definition of the Δ¹-pyrrolinesaccording to the invention.

-   R¹ preferably represents halogen, alkyl, halogenoalkyl, alkoxy,    halogenoalkoxy or —S(O)_(w)R⁴.-   R² and R³ independently of one another preferably represent    hydrogen, halogen, alkyl, halogenoalkyl, alkoxy, halogenoalkoxy or    alkoxyalkyl.-   R⁴ preferably represents alkyl or halogenoalkyl.-   Het preferably represents 5- to 14-membered heteroaryl which    comprises 1 to 3 aromatic rings and one or more heteroatoms from the    group consisting of nitrogen, oxygen and sulphur and is optionally    mono- to tetrasubstituted by identical or different R⁵.-   R⁵ preferably represents the grouping —X—Y-Z-E, with the proviso    that Y does not represent a direct bond if X does not represent a    direct bond.-   X preferably represents a direct bond, oxygen, —S(O)_(w)—, —NR⁶—,    carbonyl, carbonyloxy, oxycarbonyl, oxysulphonyl (OSO₂), alkylene,    halogenoalkylene, alkenylene, halogenoalkenylene, alkinylene,    alkyleneoxy, oxyalkylene, oxyalkyleneoxy, —S(O)_(w)-alkylene,    cyclopropylene or oxiranylene.-   Y preferably represents a direct bond or represents phenylene,    naphthylene, tetrahydronaphthylene or 5- to 10-membered saturated or    unsaturated heterocyclylene having one or more heteroatoms from the    group consisting of nitrogen, oxygen and sulphur, each of which    radicals is optionally mono- to tetrasubstituted by identical or    different radicals from the list W¹.-   Z preferably represents a direct bond or —(CH₂)_(n)—.-   E preferably represents hydrogen, halogen, hydroxyl, cyano, formyl,    nitro, trialkylsilyl, pentafluorothio, —S(O)_(w)R⁷, —OSO₂R⁷, —NR⁸R⁹,    —COR⁷, —CO₂R⁷, —OC(O)R⁷, —CONR¹⁰R¹¹, —N(R¹²)COR¹³, —C(R¹⁴)═N—OR¹⁵,    —SO₂NR¹⁶R¹⁷; represents alkyl, alkenyl, alkinyl, alkoxy, alkenyloxy,    each of which is optionally mono- or polysubstituted by identical or    different substituents from, the group consisting of halogen, cyano,    alkoxy and/or —NR⁸R⁹; or represents cycloalkyl, cycloalkylalkyl,    cycloalkyloxy, aryl, arylalkyl, aryloxy, aryloxyalkyl, saturated or    unsaturated 5- to 10-membered heterocyclyl or heterocyclylalkyl    having one or more heteroatoms from the group consisting of    nitrogen, oxygen and sulphur, each of which radicals is optionally    mono- or polysubstituted by identical or different substituents from    the group consisting of halogen, cyano, nitro, alkyl, halogenoalkyl,    alkenyl, halogenoalkenyl, alkoxy, halogenoalkoxy, alkylthio and    halogenoalkylthio.-   W¹ preferably represents halogen, cyano, formyl, nitro,    trialkylsilyl, alkyl, halogenoalkyl, alkoxy, halogenoalkoxy,    alkenyl, halogenoalkenyl, alkenyloxy, halogenoalkenyloxy,    alkylcaronyl, alkoxycarbonyl, —S(O)_(w)R⁷, —C(R¹⁴)═N—OR¹⁵,    —SO₂NR¹⁶R¹⁷, —(CH₂)_(p)NR¹⁶R¹⁷, —(CH₂)_(p)N(R¹⁶)COR¹⁷,    —(CH₂)_(p)N(R¹⁶)SO₂R¹⁷, —OSO₂R¹⁶, —OSO₂NR¹⁶R¹⁷.-   R⁶ preferably represents alkyl, halogenoalkyl or represents    cycloalkyl, cycloalkylalkyl, aryl or arylalkyl, each of which is    optionally mono- or polysubstituted by identical or different    substituents from the group consisting of halogen, alkyl,    halogenoalkyl, alkoxy, halogenoalkoxy, alkylthio and/or    halogenoalkylthio.-   R⁷ preferably represents alkyl which is optionally mono- or    polysubstituted by identical or different substituents from the    group consisting of halogen and —NR⁸R⁹, represents cycloalkyl, aryl    or arylalkyl, each of which is optionally mono- or polysubstituted    by identical or different substituents from the group consisting of    halogen, cyano, alkyl, halogenoalkyl, alkoxy, halogenoalkoxy,    alkylthio and halogenoalkylthio.-   R⁸ and R⁹ independently of one another preferably represent    hydrogen, —SO₂R⁷, —COR⁷, —CO₂R⁷, represent alkyl or alkenyl, each of    which is optionally mono- or polysubstituted by identical or    different substituents from the group consisting of halogen,    alkylcarbonyl, alkylcarbonyloxy, alkylamino, dialkylamino, alkoxy,    halogenoalkoxy, alkylthio and halogenoalkylthio; represents    cycloalkyl, cycloalkylalkyl, aryl, arylalkyl or saturated or    unsaturated 5- to 10-membered heterocyclyl or heterocyclylalkyl    having one or more heteroatoms from the group consisting of    nitrogen, oxygen and sulphur, each of which radicals is optionally    mono- or polysubstituted by identical or different substituents from    the group consisting of halogen, cyano, alkyl, halogenoalkyl,    alkoxy, halogenoalkoxy, alkylthio and halogenoalkylthio.-   R⁸ and R⁹ furthermore together preferably represent alkenylene which    is optionally mono- or polysubstituted by identical or different    substituents from the group consisting of halogen, cyano, alkoxy,    halogenoalkoxy, alkylthio and halogenoalkylthio or represent    alkylene which is optionally mono- or polysubstituted by identical    or different substituents from the group consisting of halogen,    cyano, alkyl, halogenoalkyl, alkoxy, halogenoalkoxy, alkylthio and    halogenoalkylthio, where the alkylene chain may in each case be    interrupted by —O—, —S— or —NR¹⁸—.-   R¹⁰ and R¹¹ independently of one another preferably represent    hydrogen, —SO₂R⁷, represent alkyl or alkenyl, each of which is    optionally mono- or polysubstituted by identical or different    substituents from the group consisting of halogen, alkylamino,    dialkylamino, alkoxy and alkylthio; represent cycloalkyl,    cycloalkylalkyl, aryl, arylalkyl or saturated or unsaturated 5- to    10-membered heterocyclyl or heterocyclylalkyl having one or more    heteroatoms from the group consisting of nitrogen; oxygen and    sulphur, each of which radicals is optionally mono- or    polysubstituted by identical or different substituents from the    group consisting of halogen, cyano, alkyl, halogenoalkyl, alkoxy,    halogenoalkoxy, alkylthio and halogenoalkylthio.-   R¹⁰ and R¹¹ furthermore together preferably represent alkylene which    is optionally mono- or polysubstituted by identical or different    substituents from the group consisting of halogen, cyano, alkyl,    halogenoalkyl, alkoxy, halogenoalkoxy, alkylthio and    halogenoalkylthio, where the alkylene chain may in each case be    interrupted by —O—, —S— or —NR¹⁸—.-   R¹² and R¹³ independently of one another preferably represent    hydrogen, represent alkyl which is optionally mono- or    polysubstituted by identical or different substituents from the    group consisting of cyano, alkoxy and alkylthio, represent    cycloalkyl, cycloalkylalkyl, aryl or arylalkyl, each of which is    optionally mono- or polysubstituted by identical or different    substituents from the group consisting of halogen, cyano, alkyl,    halogenoalkyl, alkoxy, halogenoalkoxy, alkylthio and    halogenoalkylthio.-   R¹² and R¹³ furthermore together preferably represent alkylene or    alkenylene, each of which is optionally mono- or polysubstituted by    identical or different substituents from the group consisting of    halogen, alkyl, halogenoalkyl, alkoxy, halogenoalkoxy, alkylthio and    halogenoalkylthio.-   R¹⁴ and R¹⁵ independently of one another preferably represent    hydrogen, represent alkyl, halogenoalkyl, alkenyl or    halogenoalkenyl.-   R¹⁶ and R¹⁷ independently of one another preferably represent    hydrogen) alkyl, halogenoalkyl or represent cycloalkyl which is    optionally mono- or polysubstituted by identical or different    substituents from the group consisting of halogen and alkyl.-   R¹⁶ and R¹⁷ furthermore together preferably represent alkylene,    alkoxyalkylene or alkylthioalkylene, each of which is optionally    mono- or polysubstituted by identical or different substituents from    the group consisting of halogen and alkyl.-   R¹⁸ preferably represents hydrogen, —SO₂R⁷, —COR⁷ or —CO₂R⁷;    represents alkyl or alkenyl, each of which is optionally mono- or    polysubstituted by identical or different substituents from the    group consisting of halogen, cyano, alkylamino, dialkylamino,    alkoxy, halogenoalkoxy, alkylthio and halogenalkylthio; represents    cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, saturated or    unsaturated 5- to 10-membered heterocyclyl or heterocyclylalkyl    having one or more heteroatoms from the group consisting of    nitrogen, oxygen and sulphur, each of which radicals is optionally    mono- or polysubstituted by identical or different substituents from    the group consisting of halogen, cyano, alkyl, halogenoalkyl,    alkoxy, halogenoalkoxy, alkylthio and halogenoalkylthio.-   w preferably represents 0, 1 or 2.-   n preferably represents 1, 2, 3 or 4.-   p preferably represents 0, 1 or 2.-   R¹ particularly preferably represents halogen, C₁–C₆-alkyl,    C₁–C₆-halogenoalkyl, C₁–C₆-alkoxy, C₁–C₆-halogenoalkoxy or    —S(O)_(w)R⁴.-   R² and R³ independently of one another particularly preferably    represent hydrogen, halogen, C₁–C₆-alkyl, C₁–C₆-halogenoalkyl,    C₁–C₆-alkoxy, C₁–C₆-halogenoalkoxy or C₁–C₆-alkoxy-C₁–C₆-alkyl.-   R⁴ particularly preferably represents C₁–C₆-alkyl or    C₁–C₆-halogenoalkyl.-   Het particularly preferably represents 5- to 14-membered heteroaryl    which comprises 1 to 3 aromatic rings and 1 to 4 heteroatoms    including 0 to 4 nitrogen atoms, 0 to 2 nonadjacent oxygen atoms    and/or 0 to 2 nonadjacent sulphur atoms (in particular thienyl,    benzothienyl, furyl, benzofuryl, indolyl, thienothienyl,    thienofuryl, thienobenzothienyl, thienobenzofuryl, pyridinyl,    pyrimidinyl, pyridazinyl, pyrazinyl, triazolyl or tetrazolyl), each    of which radicals is optionally mono- to tetrasubstituted by    identical or different R⁵.-   R⁵ particularly preferably represents the grouping —X—Y-Z-E, with    the proviso that Y does not represent a direct bond if X does not    represent a direct bond.-   X particularly preferably represents a direct bond, oxygen,    —S(O)_(w)—, —NR⁶—, carbonyl, carbonyloxy, oxycarbonyl, oxysulphonyl    (OSO₂), C₁–C₆-alkylene, C₁–C₆-halogenoalkylene, C₂–C₆-alkenylene,    C₂–C₆-halogenoalkenylene, C₂–C₆-alkinylene, C₁–C₆-alkyleneoxy,    C₁–C₆-oxyalkylene, oxy-C₁–C₆-alkyleneoxy, —S(O)_(w)—C₁–C₆-alkylene,    cyclopropylene or oxiranylene.-   Y particularly preferably represents a direct bond or represents    1,4-phenylene, 1,3-phenylene, 1,2-phenylene, 2,6-naphthylene,    2,7-naphthylene, 1,4-naphthylene,    2,6-(1,2,3,4-tetrahydro)naphthylene,    2,7-(1,2,3,4-tetrahydro)naphthylene,    1,4-(1,2,3,4-tetrahydro)naphthylene,    5,8-(1,2,3,4-tetrahydro)naphthylene, each of which is optionally    mono- to tetrasubstituted by identical or different radicals from    the list W¹; or represents 5- or 6-membered saturated or unsaturated    heterocyclylene which comprises 1 to 3 heteroatoms including 0 to 3    nitrogen atoms, 0 to 2 nonadjacent oxygen atoms and/or 0 to 2    nonadjacent sulphur atoms (in particular furylene, thienylene,    pyrrolylene, oxazolylene, thiazolylene, pyridinylene,    pyrimidinylene, pyridazinylene or pyrazinylene), each of which    radicals is optionally mono- to tetrasubstituted by identical or    different radicals from the list W¹.-   Z particularly preferably represents a direct bond or —(CH₂)_(n)—.-   E particularly preferably represents hydrogen, fluorine, chlorine,    bromine, hydroxyl, cyano, formyl, nitro, tri-(C₁–C₆-alkyl)silyl,    pentafluorothio, —S(O)_(w)R⁷, —OSO₂R⁷, —NR⁸R⁹, —COR⁷, —CO₂R⁷,    —OC(O)R⁷, —CONR¹⁰R¹¹, —N(R¹²)COR¹³, —C(R¹⁴)═N—OR¹⁵, —SO₂NR¹⁶R¹⁷;    represents C₁–C₂₀-alkyl, C₂–C₂₀-alkenyl, C₂–C₁₀-alkinyl,    C₁–C₂₀-alkoxy, C₂–C₂₀-alkenyloxy, each of which is optionally mono-    or polysubstituted by identical or different radicals from the group    consisting of halogen, cyano, C₁–C₁₀-alkoxy and —NR⁸R⁹; or    represents C₃–C₁₂-cycloalkyl, C₃–C₇-cycloalkyl-C₁–C₄-alkyl,    C₃–C₁₂-cycloalkyloxy, aryl, aryl-C₁–C₄-alkyl, aryloxy,    aryloxy-C₁–C₄-alkyl, saturated or unsaturated 5- to 10-membered    heterocyclyl or heterocyclyl-C₁–C₄-alkyl which comprises 1 to 4    heteroatoms including 0 to 4 nitrogen atoms, 0 to 2 nonadjacent    oxygen atoms and/or 0 to 2 nonadjacent sulphur atoms (in particular    tetrazolyl, furyl, furfuryl, benzofuryl, tetrahydrofuryl, thienyl,    thenyl, benzothienyl, thiolanyl, pyrrolyl, indolyl, pyrrolinyl,    pyrrolidino, pyrrolidinyl, oxazolyl, benzoxazolyl, isoxazolyl,    imidazolyl, pyrazolyl, thiazolyl, benzothiazolyl, thiazolidinyl,    pyridinyl, pyrimidinyl, pyridazyl, pyrazinyl, piperidinyl,    piperidino, morpholinyl, thiomorpholinyl, morpholino,    thiomorpholino, triazinyl, triazolyl, quinolinyl or isoquinolinyl),    each of which radicals is optionally mono- to tetrasubstituted by    identical or different substituents from the group consisting of    halogen, cyano, nitro, C₁–C₆-alkyl, C₁–C₆-halogenoalkyl,    C₂–C₆-alkenyl, C₂–C₆-halogenoalkenyl, C₁–C₆-alkoxy,    C₁–C₆-halogenoalkoxy, C₁–C₆-alkylthio and C₁–C₆-halogenoalkylthio.-   W¹ particularly preferably represents fluorine, chlorine, bromine,    cyano, formyl, nitro, tri-(C₁–C₆-alkyl)silyl, C₁–C₆-alkyl,    C₁–C₆-halogenoalkyl, C₁–C₆-alkoxy, C₁–C₆-halogenoalkoxy,    C₂–C₆-alkenyl, C₂–C₆-halogenoalkenyl, C₂–C₆-alkenyloxy,    C₂–C₆-halogenoalkenyloxy, C₁–C₆-alkylcarbonyl, C₁–C₆-alkoxycarbonyl,    —S(O)_(w)R⁷, —C(R¹⁴)═N—OR¹⁵, —SO₂NR¹⁶R¹⁷, —(CH₂)_(p)NR¹⁶R¹⁷,    —(CH₂)_(p)N(R¹⁶)COR¹⁷, —(CH₂)_(p)N(R¹⁶)SO₂R¹⁷, —OSO₂R¹⁶,    —OSO₂NR¹⁶R¹⁷.-   R⁶ particularly preferably represents C₁–C₆-alkyl,    C₁–C₆-halogenoalkyl or represents C₃–C₇-cycloalkyl,    C₃–C₆-cycloalkyl-C₁–C₄-alkyl, aryl or aryl-C₁–C₄-alkyl, each of    which is optionally mono- to tetrasubstituted by halogen,    C₁–C₆-alkyl, C₁–C₆-halogenoalkyl, C₁–C₆-alkoxy,    C₁–C₆-halogenoalkoxy, C₁–C₆-alkylthio and C₁–C₆-halogenoalkylthio.-   R⁷ particularly preferably represents C₁–C₂₀-alkyl which is    optionally mono- or polysubstituted by identical or different    substituents from the group consisting of halogen and —NR⁸R⁹,    represents C₃–C₆-cycloalkyl, aryl or aryl-C₁–C₄-alkyl, each of which    is optionally mono- to octasubstituted by identical or different    substituents from the group consisting of halogen, cyano,    C₁–C₆-alkyl, C₁–C₆-halogenoalkyl, C₁–C₆-alkoxy,    C₁–C₆-halogenoalkoxy, C₁–C₆-alkylthio and C₁–C₆-halogenoalkylthio.-   R⁸ and R⁹ independently of one another particularly preferably    represent hydrogen, —SO₂R⁷, —COR⁷, —CO₂R⁷, represent C₁–C₂₀-alkyl or    C₂–C₂₀-alkenyl, each of which is optionally mono- or polysubstituted    by identical or different substituents from the group consisting of    halogen, C₁–C₆-alkylcarbonyl, C₁–C₆-alkylcarbonyloxy,    C₁–C₆-alkylamino, di-(C₁–C₆-alkyl)amino, C₁–C₆-alkoxy,    C₁–C₆-halogenoalkoxy, C₁–C₆-alkylthio, C₁–C₆-halogenoalkylthio;    represent C₃–C₁₂-cycloalkyl, C₃–C₇-cycloalkyl-C₁–C₄-alkyl, aryl,    aryl-C₁–C₄-alkyl or saturated or unsaturated 5- to 10-membered    heterocyclyl or heterocyclyl-C₁–C₄-alkyl which comprises 1 to 4    heteroatoms including 0 to 4 nitrogen atoms, 0 to 2 nonadjacent    oxygen atoms and/or 0 to 2 nonadjacent sulphur atoms (in particular    tetrazolyl, furyl, furfuryl, benzofuryl, tetrahydrofuryl, thienyl,    thenyl, benzothienyl, thiolanyl, pyrrolyl, indolyl, pyrrolinyl,    pyrrolidinyl, oxazolyl, benzoxazolyl, isoxazolyl, imidazolyl,    pyrazolyl, thiazolyl, benzothiazolyl, thiazolidinyl, pyridinyl,    pyrimidinyl, pyridazyl, pyrazinyl, piperidinyl, morpholinyl,    thiomorpholinyl, triazinyl, triazolyl, quinolinyl or isoquinolinyl),    each of which radicals is optionally mono- to tetrasubstituted by    identical or different substituents from the group consisting of    halogen, cyano, C₁–C₆-alkyl, C₁–C₆-halogenoalkyl, C₁–C₆-alkoxy,    C₁–C₆-halogenoalkoxy, C₁–C₆-alkylthio or C₁–C₆-halogenoalkylthio.-   R⁸ and R⁹ furthermore together particularly preferably represent    C₂–C₁₂-alkenylene which is optionally mono- or polysubstituted by    identical or different substituents from the group consisting of    halogen, cyano, C₁–C₆-alkoxy, C₁-C₆-halogenoalkoxy, C₁–C₆-alkylthio    and C₁–C₆-halogenoalkylthio or represent C₃–C₁₂-alkylene which is    optionally mono- or polysubstituted in the alkylene moiety by    identical or different substituents from the group consisting of    halogen, cyano, C₁–C₆-alkyl, C₁–C₆-halogenoalkyl, C₁–C₆-alkoxy,    C₁–C₆-halogenoalkoxy, C₁–C₆-alkylthio and C₁–C₆-halogenoalkylthio,    where the alkylene chain may in each case be interrupted by —O—, —S—    or —NR⁸—.-   R¹⁰ and R¹¹ independently of one another particularly preferably    represent hydrogen, —SO₂R⁷, represent C₁–C₆-alkyl or C₂–C₆-alkenyl,    each of which is optionally mono- to tridecasubstituted by identical    or different substituents from the group consisting of halogen,    C₁–C₆-alkylamino, di-(C₁–C₆-alkyl)amino, C₁–C₆-alkoxy,    C₁–C₆-halogenoalkoxy, C₁–C₆-alkylthio and C₁–C₆-halogenoalkylthio;    represent C₃–C₇-cycloalkyl, C₃–C₇-cycloalkyl-C₁–C₄-alkyl, aryl,    aryl-C₁–C₄-alkyl or saturated or unsaturated 5- to 10-membered    heterocyclyl or heterocyclyl-C₁–C₄-alkyl which comprises 1 to 4    heteroatoms including 0 to 4 nitrogen atoms, 0 to 2 nonadjacent    oxygen atoms and/or 0 to 2 nonadjacent sulphur atoms (in particular    tetrazolyl, furyl, furfuryl, benzofuryl, tetrahydrofuryl, thienyl,    thenyl, benzothienyl, thiolanyl, pyrrolyl, indolyl, pyrrolinyl,    pyrrolidinyl, oxazolyl, benzoxazolyl, isoxazolyl, imidazolyl,    pyrazolyl, thiazolyl, benzothiazolyl, thiazolidinyl, pyridinyl,    pyrimidinyl, pyridazyl, pyrazinyl, piperidinyl, morpholinyl,    thiomorpholinyl, triazinyl, triazolyl, quinolinyl or isoquinolinyl),    each of which radicals is optionally mono- to tetrasubstituted by    identical or different substituents from the group consisting of    halogen, cyano, C₁–C₆-alkyl, C₁–C₆-halogenoalkyl, C₁–C₆-alkoxy,    C₁–C₆-halogenoalkoxy, C₁–C₆-alkylthio and C₁–C₆-halogenoalkylthio.-   R¹⁰ and R¹¹ furthermore together particularly preferable represent    C₃–C₆-alkylene, —(CH₂)₂—O—(CH₂)₂—, —(CH₂)₂—S—(CH₂)₂— or    —(CH₂)₂—N(R¹⁸)—(CH₂)₂—, each of which is optionally mono- to    tetrasubstituted in the alkylene moiety by identical or different    substituents from the group consisting of halogen, cyano,    C₁–C₆-alkyl, C₁–C₆-halogenoalkyl, C₁–C₆-alkoxy,    C₁–C₆-halogenoalkoxy, C₁–C₆-alkylthio and C₁–C₆-halogenoalkylthio.-   R¹² and R¹³ independently of one another particularly preferably    represent hydrogen, represent C₁–C₆-alkyl which is optionally mono-    to tridecasubstituted by identical or different substituents from    the group consisting of halogen, cyano, C₁–C₆-alkoxy and    C₁–C₆-alkylthio, represent C₃–C₇-cycloalkyl,    C₃–C₇-cycloalkyl-C₁–C₄-alkyl, aryl or aryl-C₁–C₄-alkyl, each of    which is optionally mono- to octasubstituted by identical or    different substituents from the group consisting of halogen, cyano,    C₁–C₆-alkyl, C₁–C₆-halogenoalkyl, C₁–C₆-alkoxy,    C₁–C₆-halogenoalkoxy, C₁–C₆-alkylthio and C₁–C₆-halogenoalkylthio.-   R¹² and R¹³ furthermore together particularly preferably represent    C₃–C₁₀-alkylene or C₃–C₁₀-alkenylene, each of which is optionally    mono- to octasubstituted by identical or different substituents from    the group consisting of halogen, C₁–C₆-alkyl, C₁–C₆-halogenoalkyl,    C₁–C₆-alkoxy, C₁–C₆-halogenoalkoxy, C₁–C₆-alkylthio and    C₁–C₆-halogenoalkylthio.-   R¹⁴ and R¹⁵ independently of one another particularly-preferably    represent hydrogen, represent C₁–C₆-alkyl, C₁–C₆-halogenoalkyl,    C₂–C₆-alkenyl or C₂–C₆-halogenoalkenyl.-   R¹⁶ and R¹⁷ independently of one another particularly preferably    represent hydrogen, C₁–C₆-alkyl, C₁–C₆-halogenoalkyl or represent    C₃–C₇-cycloalkyl which is optionally mono- to octasubstituted by    identical or different substituents from the group consisting of    fluorine, chlorine, bromine and/or C₁–C₆-alkyl.-   R¹⁶ and R¹⁷ furthermore together particularly preferably represent    C₃–C₆-alkylene, C₁–C₃-alkoxy-C₁–C₃-alkylene or    C₁–C₃-alkylthio-C₁–C₃-alkylene, each of which is optionally mono- to    nonasubstituted by identical or different substituents from the    group consisting of fluorine, chlorine, bromine and C₁–C₆-alkyl.-   R¹⁸ particularly preferably represents hydrogen, —SO₂R⁷, —COR⁷ or    —CO₂R⁷; represents C₁–C₂₀-alkyl or C₂–C₂₀-alkenyl, each of which is    optionally mono- or polysubstituted by identical or different    substituents from the group consisting of halogen, cyano,    C₁–C₆-alkylamino, di-(C₁–C₆-alkyl)amino, C₁–C₆-alkoxy,    C₁–C₆-halogenoalkoxy, C₁–C₆-alkylthio and C₁–C₆-halogenoalkylthio;    represents C₃–C₁₂-cycloalkyl, C₃–C₇-cycloalkyl-C₁–C₄-alkyl, aryl,    aryl-C₁–C₄-alkyl, saturated or unsaturated 5- to 10-membered    heterocyclyl or heterocyclyl-C₁–C₄-alkyl which comprises 1 to 4    heteroatoms including 0 to 4 nitrogen atoms, 0 to 2 nonadjacent    oxygen atoms and/or 0 to 2 nonadjacent sulphur atoms (in particular    tetrazolyl, furyl, furfuryl, benzofuryl, tetrahydrofuryl, thienyl,    thenyl, benzothienyl, thiolanyl, pyrrolyl, indolyl, pyrrolinyl,    pyrrolidinyl, oxazolyl, benzoxazolyl, isoxazolyl, imidazolyl,    pyrazolyl, thiazolyl, benzothiazolyl, thiazolidinyl, pyridinyl,    pyrimidinyl, pyridazyl, pyrazinyl, piperidinyl, morpholinyl,    thiomorpholinyl, triazinyl, triazolyl, quinolinyl or isoquinolinyl),    each of which radicals is optionally mono- to tetrasubstituted by    identical or different substituents from the group consisting of    halogen, cyano, C₁–C₆-alkyl, C₁–C₆-halogenoalkyl, C₁–C₆-alkoxy,    C₁–C₆-halogenoalkoxy, C₁–C₆-alkylthio and C₁–C₆-halogenoalkylthio.-   w particularly preferably represents 0, 1 or 2.-   n particularly preferably represents 1, 2 or 3.-   p particularly preferably represents 0, 1 or 2.-   R¹ very particularly preferably represents fluorine, chlorine,    bromine, C₁–C₄-alkyl, C₁–C₄-halogenoalkyl having 1 to 9 fluorine,    chlorine and/or bromine atoms, C₁–C₄-alkoxy, C₁–C₄-halogenoalkoxy    having 1 to 9 fluorine, chlorine and/or bromine atoms or    —S(O)_(w)R⁴.-   R² and R³ independently of one another very particularly preferably    represent hydrogen, fluorine, chlorine, bromine, C₁–C₄-alkyl,    C₁–C₄-halogenoalkyl having 1 to 9 fluorine, chlorine and/or bromine    atoms, C₁–C₄-alkoxy or C₁–C₄-halogenoalkoxy having 1 to 9 fluorine,    chlorine and/or bromine atoms.-   R⁴ very particularly preferably represents C₁–C₄-alkyl or represents    in each case fluorine- or chlorine-substituted methyl or ethyl.-   Het very particularly preferably represents 2-thienyl, 3-thienyl,    2-benzo[b]thienyl, 2-furyl, 3-furyl, 2-benzo[b]furyl, 2-indolyl,    2-thieno[3,2-b]thienyl, 2-thieno[3,2-b]furyl, 5-thieno[3,2-b]furyl,    2-thieno[2,3-f][1]benzothienyl, 2-thieno[2,3-f][1]benzofuryl,    6-thieno[2,3-f][1]benzofuryl, 2-pyridinyl, 3-pyridinyl,    2-pyrimidinyl, 5-pyrimidinyl, 3-pyridazinyl, 4-pyridazinyl,    2-pyrazinyl, triazolyl or tetrazolyl, each of which is optionally    mono- to trisubstituted by identical or different R⁵.-   R⁵ very particularly preferably represents the grouping —X—Y-Z-E,    with the proviso that Y does not represent a direct bond if X does    not represent a direct bond.-   X very particularly preferably represents a direct bond, oxygen    —S(O)_(w)—, —NR⁶—, carbonyl, carbonyloxy, oxycarbonyl, oxysulphonyl    (OSO₂), C₁–C₄-alkylene, C₁–C₄-halogenoalkylene having 1 to 8    fluorine, chlorine and/or bromine atoms, C₂–C₄-alkenylene,    C₂–C₄-halogenoalkenylene having 1 to 6 fluorine, chlorine and/or    bromine atoms, C₂–C₄-alkinylene, C₁–C₄-alkyleneoxy,    oxy-C₁–C₄-alkylene, oxy-C₁–C₄-alkyleneoxy or    —S(O)_(w)—C₁–C₄-alkylene.-   Y very particularly preferably represents a direct bond or    represents 1,4-phenylene, 1,3-phenylene, 1,2-phenylene,    2,6-naphthylene, 2,7-naphthylene, 1,4-naphthylene,    2,6-(1,2,3,4-tetrahydro)naphthylene,    2,7-(1,2,3,4-tetrahydro)naphthylene,    1,4-(1,2,3,4-tetrahydro)naphthylene,    5,8-(1,2,3,4-tetrahydro)naphthylene, 2,4-furylene, 2,4-thienylene,    2,4-pyrrolylene, 2,5-oxazolylene, 2,5-thiazolylene,    2,5-pyridinylene, 2,6-pyridinylene, 2,5-pyrimidinylene,    3,6-pyridazinylene or 2,5-pyrazinylene, each of which is optionally    mono- to trisubstituted by identical or different radicals from the    list W¹.-   Z very particularly preferably represents a direct bond or    —(CH₂)_(n)—.-   E very particularly preferably represents hydrogen, fluorine,    chlorine, bromine, hydroxyl, cyano, formyl, nitro, trimethylsilyl,    dimethyl-tert-butylsilyl, —S(O)_(w)R⁷, —OSO₂R⁷, —NR⁸R⁹, —COR⁷,    —CO₂R⁷, —OC(O)R⁷, —CONR¹⁰R¹¹, —N(R¹²)COR¹³, —SO₂NR¹⁶R¹⁷; represents    C₁–C₁₆-alkyl, C₂–C₁₆-alkenyl, C₂–C₆-alkinyl, C₁–C₁₆-alkoxy,    C₂–C₁₆-alkenyloxy, each of which is optionally mono- or    polysubstituted by identical or different substituents from the    group consisting of fluorine, chlorine, bromine, cyano, C₁–C₆-alkoxy    and —NR⁸R⁹; or represents C₃–C₁₀-cycloalkyl,    C₃–C₆-cycloalkyl-C₁–C₄-alkyl, C₃–C₁₀-cycloalkyloxy, phenyl, phenoxy,    benzyl, phenylethyl, benzyloxy, tetrazolyl, furyl, furfuryl,    benzofuryl, tetrahydrofuryl, thienyl, thenyl, benzothienyl,    thiolanyl, pyrrolyl, indolyl, pyrrolinyl, pyrrolidino, pyrrolidinyl,    oxazolyl, benzoxazolyl, isoxazolyl, imidazolyl, pyrazolyl,    thiazolyl, benzothiazolyl, thiazolidinyl, pyridinyl, pyrimidinyl,    pyridazyl, pyrazinyl, piperidinyl, piperidino, morpholinyl,    thiomorpholinyl, morpholino, thiomorpholino, triazinyl, triazolyl,    quinolinyl or isoquinolinyl, each of which is optionally mono- to    trisubstituted by identical or different substituents from the group    consisting of fluorine, chlorine, bromine, cyano, C₁–C₄-alkyl,    C₁–C₄-halogenoalkyl, C₂–C₆-alkenyl, C₂–C₆-halogenoalkenyl,    C₁–C₄-alkoxy, C₁–C₄-halogenoalkoxy, C₁–C₄-alkylthio and    C₁–C₄-halogenoalkylthio.-   W¹ very particularly preferably represents fluorine, chlorine,    bromine, cyano, formyl; trimethylsilyl, dimethyl-tert-butylsilyl,    C₁–C₄-alkyl, C₁–C₄-alkoxy, C₂–C₄-alkenyl, C₂–C₄-alkenyloxy;    represents C₁–C₄-halogenoalkyl, C₁–C₄-halogenoalkoxy having in each    case 1 to 9 fluorine, chlorine and/or bromine atoms,    C₂–C₄-halogenoalkenyl, C₂–C₄-halogenoalkenyloxy having in each case    1 to 8 fluorine, chlorine and/or bromine atoms; represents    C₁–C₄-alkylcarbonyl, C₁–C₄-alkoxycarbonyl, —S(O)_(w)R⁷, —SO₂NR¹⁶R¹⁷,    —(CH₂)_(p)NR¹⁶R¹⁷, —(CH₂)_(p)N(R¹⁶)COR¹⁷, —(CH₂)_(p)N(R¹⁶)SO₂R¹⁷,    —OSO₂R¹⁶, —OSO₂NR¹⁶R¹⁷.-   R⁶ very particularly preferably represents methyl, ethyl, n-propyl,    isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl,    trifluoromethyl, trifluoroethyl, or represents cyclopropyl,    cyclopropylmethyl, cyclopentyl, cyclopentylmethyl, cyclohexyl,    cyclohexylmethyl, phenyl, benzyl or phenylethyl, each of which is    optionally mono- to tetrasubstituted by identical or different    substituents from the group consisting of fluorine, chlorine, brome,    C₁–C₄-alkyl, C₁–C₄-alkoxy, C₁–C₄-alkylthio, C₁–C₄-halogenoalkyl,    C₁–C₄-halogenoalkoxy and C₁–C₄-halogenoalkylthio having in each case    1 to 9 fluorine, chlorine and/or bromine atoms.-   R⁷ very particularly preferably represents C₁–C₁₀-alkyl which is    optionally mono- or polysubstituted by identical or different    substituents from the, group consisting of fluorine, chlorine,    bromine and —NR⁸R⁹, represents cyclopropyl, cyclopentyl, cyclohexyl,    phenyl or benzyl, each of which is optionally mono- to    tetrasubstituted by identical or different substituents from the    group consisting of fluorine, chlorine, bromine, cyano, C₁–C₄-alkyl,    C₁–C₄-alkoxy, C₁–C₄-alkylthio, C₁–C₄-halogenoalkyl,    C₁–C₄-halogenoalkoxy and C₁–C₄-halogenoalkylthio.-   R⁸ and R⁹ independently of one another very particularly preferably    represent hydrogen, —SO₂R⁷, —COR⁷, —CO₂R⁷, represent C₁–C₁₆-alkyl or    C₂–C₁₆-alkenyl, each of which is optionally mono- or polysubstituted    by identical or different substituents from the group consisting of    fluorine, chlorine, bromine, C₁–C₄-alkylcarbonyl,    C₁–C₄-alkylcarbonyloxy, C₁–C₄-alkylamino, di-(C₁–C₄-alkyl)-amino,    C₁–C₄-alkoxy, C₁–C₄-halogenoalkoxy, C₁–C₄-alkylthio and    C₁–C₄-halogenoalkylthio; represent C₃–C₁₀-cycloalkyl,    C₃–C₆-cycloalkyl-C₁–C₄-alkyl, phenyl, benzyl, phenylethyl,    tetrazolyl, furyl, furfuryl, benzofuryl, tetrahydrofuryl, thienyl,    thenyl, benzothienyl, thiolanyl, pyrrolyl, indolyl, pyrrolinyl,    pyrrolidinyl, oxazolyl, benzoxazolyl, isoxazolyl, imidazolyl,    pyrazolyl, thiazolyl, benzothiazolyl, thiazolidinyl, pyridinyl,    pyrimidinyl, pyridazyl, pyrazinyl, piperidinyl, morpholinyl,    thiomorpholinyl, triazinyl, triazolyl, quinolinyl or isoquinolinyl,    each of which is optionally mono- to trisubstituted by identical or    different substituents from the group consisting of fluorine,    chlorine, bromine, cyano, C₁–C₄-alkyl, C₁–C₄-halogenoalkyl,    C₁–C₄-alkoxy, C₁–C₄-halogenoalkoxy, C₁–C₄-alkylthio and    C₁–C₄-halogenoalkylthio.-   R⁸ and R⁹ furthermore together very particularly preferably    represent C₂–C₁₀-alkenylene which is optionally mono- or    polysubstituted by identical or different substituents from the    group consisting of fluorine, chlorine, bromine, C₁–C₄-alkoxy,    C₁–C₄-halogenoalkoxy, C₁–C₄-alkylthio and C₁–C₄-halogenoalkylthio or    represent C₃–C₁₀-alkylene, which is optionally mono- or    polysubstituted in the alkylene moiety by identical or different    substituents from the group consisting of fluorine, chlorine, cyano,    C₁–C₄-alkyl, C₁–C₄-halogenoalkyl, C₁–C₄-alkoxy,    C₁–C₄-halogenoalkoxy, C₁–C₄-alkylthio and C₁–C₄-halogenoalkylthio,    where the alkylene chain may in each case be interrupted by —O—, —S—    or —NR¹⁸—.-   R¹⁰ and R¹¹ independently of one another very particularly    preferably represent hydrogen, —SO₂R⁷, represent C₁–C₆-alkyl or    C₂–C₆-alkenyl, each of which is optionally mono- to nonasubstituted    by identical or different substituents from the group consisting of    fluorine, chlorine, bromine, C₁–C₄-alkylamino,    di-(C₁–C₄-alkyl)amino, C₁–C₄-alkoxy, C₁–C₄-halogenoalkoxy,    C₁–C₄-alkylthio and C₁–C₄-halogenoalkylthio; represent    C₃–C₆-cycloalkyl, C₃–C₆-cycloalkyl-C₁–C₄-alkyl, phenyl, benzyl,    phenylethyl, tetrazolyl, furyl, furfuryl, benzofuryl,    tetrahydrofuryl, thienyl, thenyl, benzothienyl, thiolanyl, pyrrolyl,    indolyl, pyrrolinyl, pyrrolidinyl, oxazolyl, benzoxazolyl,    isoxazolyl, imidazolyl, pyrazolyl, thiazolyl, benzothiazolyl,    thiazolidinyl, pyridinyl, pyrimidinyl, pyridazyl, pyrazinyl,    piperidinyl, morpholinyl, thiomorpholinyl, triazinyl, triazolyl,    quinolinyl or isoquinolinyl, each of which is optionally mono- to    trisubstituted by identical or different substituents from the group    consisting of fluorine, chlorine, bromine, cyano, C₁–C₄ alkyl,    C₁–C₄-halogenoalkyl, C₁–C₄-alkoxy, C₁–C₄-halogenoalkoxy,    C₁–C₄-alkylthio and C₁–C₄-halogenoalkylthio.-   R¹⁰ and R¹¹ furthermore together very particularly preferably    represent C₄–C₆-alkylene, —(CH₂)₂—O—(CH₂)₂—, —(CH₂)₂—S—(CH₂)₂— or    —(CH₂)—N(R¹⁸)—(CH₂)₂—, each of which is optionally mono- to    tetrasubstituted in the alkylene-moiety by identical or different    substituents from the group consisting of fluorine, chlorine, cyano,    C₁–C₄-alkyl, C₁–C₄-halogenoalkyl, C₁–C₄-alkoxy,    C₁–C₄-halogenoalkoxy, C₁–C₄-alkylthio and C₁–C₄-halogenoalkylthio.-   R¹² and R¹³ independently of one another very particularly    preferably represent hydrogen, represent C₁–C₆-alkyl which is    optionally mono- to nonasubstituted by identical or different    substituents from the group consisting of fluorine, chlorine,    bromine, C₁–C₄-alkoxy and C₁–C₄-alkylthio, represent    C₃–C₆-cycloalkyl, C₃–C₆-cycloalkyl-C₁–C₄-alkyl, phenyl, benzyl or    phenylethyl, each of which is optionally mono- to tetrasubstituted    by identical or different substituents from the group consisting of    fluorine, chlorine, bromine, C₁–C₄-alkyl, C₁–C₄-halogenoalkyl,    C₁–C₄-alkoxy, C₁–C₄-halogenoalkoxy, C₁–C₄-alkylthio and    C₁–C₄-halogenoalkylthio.-   R¹² and R¹³ furthermore together very particularly preferably    represent C₃–C₈-alkylene or C₃–C₈-alkenylene, each of which is    optionally mono- to tetrasubstituted by identical or different    substituents from the group consisting of fluorine, chlorine,    bromine, C₁–C₄-alkyl, C₁–C₄-halogenoalkyl, C₁–C₄-alkoxy,    C₁–C₄-halogenoalkoxy, C₁–C₄-alkylthio and C₁–C₄-halogenoalkylthio.-   R¹⁶ and R¹⁷ independently of one another very particularly    preferably represent hydrogen, C₁–C₆-alkyl, C₁–C₄-halogenoalkyl    having 1 to 9 fluorine, chlorine and/or bromine atoms or represent    C₃–C₆-cycloalkyl which is optionally mono- to tetrasubstituted by    identical or different substituents from the group consisting of    fluorine, chlorine; bromine and C₁–C₄-alkyl.-   R¹⁶ and R¹⁷ furthermore together very particularly preferably    represent —(CH₂)₃—, —(CH₂)₄—, —(CH₂)₅—, —(CH₂)₂—O—(CH₂)₂— or    —(CH₂)₂—S—(CH₂)₂—.-   R¹⁸ very particularly preferably represents hydrogen, —SO₂R⁷,    represents —COR⁷ or —CO₂R⁷; represents C₁–C₁₆-alkyl or    C₂–C₁₆-alkenyl, each of which is optionally mono- or polysubstituted    by identical or different substituents from the group consisting of    fluorine, chlorine, bromine, cyano, methylamino, ethylamino,    di-(C₁–C₆-alkyl)amino, C₁–C₄-alkoxy, C₁–C₄-halogenoalkoxy,    C₁–C₄-alkylthio and C₁–C₄-halogenoalkylthio; represents    C₃–C₁₀-cycloalkyl, C₃–C₆-cycloalkyl-C₁–C₄-alkyl, phenyl, benzyl,    phenylethyl, tetrazolyl, furyl, furfuryl, benzofuryl,    tetrahydrofuryl, thienyl, thenyl, benzothienyl, thiolanyl, pyrrolyl,    indolyl, pyrrolinyl, pyrrolidinyl, oxazolyl, benzoxazolyl,    isoxazolyl, imidazolyl, pyrazolyl, thiazolyl, benzothiazolyl,    thiazolidinyl, pyridinyl, pyrimidinyl, pyridazyl, pyrazinyl,    piperidinyl, morpholinyl, thiomorpholinyl, triazinyl, triazolyl,    quinolinyl or isoquinolinyl, each of which is optionally mono- to    trisubstituted by identical or different substituents from the group    consisting of fluorine, chlorine, bromine, cyano, C₁–C₄-alkyl,    C₁–C₄-halogenoalkyl C₁–C₄-alkoxy, C₁–C₄-halogenoalkoxy,    C₁–C₄-alkylthio and C₁–C₄-halogenoalkylthio.-   w very particularly preferably represents 0, 1 or 2.-   n very particularly preferably represents 1 or 2.-   p very particularly preferably represents 0 or 1.-   R¹ especially preferably represents fluorine, chlorine, bromine,    methyl, trifluoromethyl, methoxy, trifluoromethoxy, methylthio or    trifluoromethylthio.-   R² and R³ independently of one another especially preferably    represent hydrogen, fluorine, chlorine, bromine, methyl,    trifluoromethyl, methoxy or trifluoromethoxy.-   Het especially preferably represents 2-thienyl, 3-thienyl,    2-benzo[b]thienyl, 2-furyl, 3-furyl, 2-benzo[b]furyl,    2-thieno[3,2-b]thienyl, 2-thieno[3,2-b]furyl, 5-thieno[3,2-b]furyl,    2-thieno[2,3-f][1]benzothienyl, 2-thieno[2,3-f][1]benzofuryl,    6-thieno[2,3-f][1]benzofuryl, 2-pyridinyl, 3-pyridinyl,    2-pyrimidinyl, 5-pyrimidinyl, 3-pyridazinyl, 4-pyridazinyl or    2-pyrazinyl, each of which is optionally mono- or disubstituted by    identical or different R⁵.-   R⁵ especially preferably represents the grouping —X—Y-Z-E, with the    proviso that Y does not represent a direct bond if X does not    represent a direct bond.-   X especially preferably represents a direct bond, oxygen, sulphur,    —SO₂—, —NR⁶—, —CO—, —C(O)—O—, —O—C(O)—, —CH₂—, —(CH₂)₂—, —C═C— (E or    Z), —C≡C—, —CH₂O—, —(CH₂)₂O—, —OCH₂—, —O(CH₂)₂—, —O—CH₂—O—, —SCH₂—,    —S(CH₂)₂—, —CH₂S— or —(CH₂)₂S—.-   Y especially preferably represents a direct bond or represents    1;4-phenylene, 1,3-phenylene, 2,6-naphthylene, 2,7-naphthylene,    2,4-furylene, 2,4-thienylene, 2,5-pyridinylene, 2,5-pyrimidinylene,    3,6-pyridazinylene or 2,5-pyrazinylene, each of which is optionally    mono- or disubstituted by identical or different radicals from the    list W¹.-   Z especially preferably represents a direct bond, methylene or    ethylene.-   E especially preferably represents hydrogen, fluorine, chlorine,    bromine, hydroxyl, cyano, formyl, —S(O)_(w)R⁷, —OSO₂R⁷, —NR⁸R⁹,    —COR⁷, —CO₂R⁷, —OC(O)R⁷, —CONR¹⁰R¹¹, —N(R¹²)COR¹³, —SO₂NR¹⁶R¹⁷;    represents C₁–C₁₆alkyl, C₂–C₁₆-alkenyl, C₁–C₁₆-alkoxy,    C₂–C₁₆-alkenyloxy, each of which is optionally mono- or    polysubstituted by identical or different substituents from the    group consisting of fluorine, chlorine, bromine, cyano, C₁–C₆-alkoxy    and —NR⁸R⁹; or represents cyclopropyl, cyclopentyl, cyclohexyl,    cyclopropyloxy, cyclopentyloxy, cyclohexyloxy, cyclopropylmethyl,    cyclopentylmethyl, cyclohexylmethyl, phenyl, phenoxy, benzyl,    phenylethyl, benzyloxy, tetrazolyl, furyl, furfuryl, benzofuryl,    tetrahydrofuryl, thienyl, thenyl, benzothienyl, thiolanyl, pyrrolyl,    indolyl, pyrrolinyl, pyrrolidino, pyrrolidinyl, oxazolyl,    benzoxazolyl, isoxazolyl, imidazolyl, pyrazolyl, thiazolyl,    benzothiazolyl, thiazolidinyl, pyridinyl, pyrimidinyl, pyridazyl,    pyrazinyl, piperidinyl, piperidino, morpholinyl, thiomorpholinyl,    morpholino, thiomorpholino, triazinyl, triazolyl, quinolinyl or    isoquinolinyl, each of which is optionally mono- to trisubstituted    by identical or different substituents from the group consisting of    fluorine, chlorine, bromine, cyano, methyl, ethyl, n-propyl,    isopropyl, —CF₃, —CHF₂, —CClF₂, —CF₂CHFCl, —CF₂CH₂F, —CF₂CCl₃,    —CH₂CF₃, —CF₂CHFCF₃, —CH₂CF₂H, —CH₂CF₂CF₃, —CF₂CF₂H, —CF₂CHFCF₃,    vinyl, allyl, 1-propenyl, butenyl, —CF═CHF, —CF═CH₂, —CF═CCl₂,    —CH═CF₂, —CF₂CF═CF₂, —CH═CFH, —CH₂CF═CF₂, —CF═CF₂, —CF₂CH═CF₂,    methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy,    sec-butoxy, tert-butoxy, trifluoromethoxy, difluoromethoxy,    chlorodifluoromethoxy, trifluoroethoxy, methylthio, ethylthio,    n-propylthio, isopropylthio, n-butylthio, isobutylthio,    sec-butylthio, tert-butylthio, trifluoromethylthio,    difluoromethylthio, chlorodifluoromethylthio and trifluoroethylthio.-   W¹ especially preferably represents fluorine, chlorine, bromine,    cyano, formyl, methyl, ethyl, n-propyl, isopropyl, n-butyl,    isobutyl, sec-butyl, tert-butyl, methoxy, ethoxy, n-propoxy,    isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, vinyl,    allyl, trifluoromethyl, trifluoroethyl, trifluoromethoxy,    trifluoroethoxy, —OCF₂CF₂H, —CH═CF₂, —CH═CCl₂, —OCF═CF₂, —COMe,    —COEt, —CO₂Me, —CO₂Et, —CO₂(t-Bu), —SMe, —SOMe, —SO₂Me, —SCF₃,    —SOCF₃, —SO₂CF₃, —SCHF₂, —SOCHF₂, —SO₂CHF₂, —SO₂NMe₂, —NMe₂, —NEt₂,    —N(n-Pr)₂, —N(Me)COMe, —N(Me)COEt, —N(Me)COPr, —N(Me)CO(t-Bu),    2-pyrrolidonyl, 2-piperidonyl, —N(Me)SO₂Me, —N(Me)SO₂Et,    —N(Me)SO₂CF₃, —N(Et)SO₂CF₃, —N(Me)SO₂(CF₂)₃CF₃ or —OSO₂NMe₂;-   R⁶ especially preferably represents methyl, ethyl, n-propyl,    isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl,    trifluoromethyl, trifluoroethyl, cyclopropyl, cyclopropylmethyl,    cyclopentyl, cyclopentylmethyl, cyclohexyl, cyclohexylmethyl,    phenyl, benzyl or phenylethyl.-   R⁷ especially preferably represents methyl, ethyl, n-propyl,    isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl,    —CF₃, —CHF₂, —CCl₃, —CCl₂F, dimethylaminomethyl, dimethylaminoethyl,    diethylaminomethyl, diethylaminoethyl, cyclopropyl, cyclopentyl,    cyclohexyl, phenyl or benzyl.-   R⁸ and R⁹ independently of one another especially preferably    represent hydrogen, —SO₂R⁷, —COR⁷, —CO₂R⁷, represent C₁–C₁₆-alkyl or    C₂–C₁₆-alkenyl, each of which is optionally mono- or polysubstituted    by identical or different substituents from the group consisting of    fluorine, chlorine, bromine, C₁–C₄-alkylcarbonyl,    C₁–C₄-alkylcarbonyloxy, C₁–C₄-alkylamino, di-(C₁–C₄-alkyl)amino,    C₁–C₄-alkoxy, C₁–C₄-halogenoalkoxy, C₁–C₄-alkylthio and    C₁–C₄-halogenoalkylthio; represent C₃–C₈-cycloalkyl,    cyclopropylmethyl, cyclopentylmethyl, cyclohexylmethyl,    cyclopropylethyl, cyclopentylethyl, cyclohexylethyl, phenyl, benzyl,    phenylethyl, tetrazolyl, furyl, furfuryl, benzofuryl,    tetrahydrofuryl, thienyl, thenyl, benzothienyl, thiolanyl, pyrrolyl,    indolyl, pyrrolinyl, pyrrolidinyl, oxazolyl, benzoxazolyl,    isoxazolyl, imidazolyl, pyrazolyl, thiazolyl, benzothiazolyl,    thiazolidinyl, pyridinyl, pyrimidinyl, pyridazyl, pyrazinyl,    piperidinyl, morpholinyl, thiomorpholinyl, triazinyl, triazolyl,    quinolinyl or isoquinolinyl, each of which is optionally mono- to    trisubstituted by identical or different substituents from the group    consisting of fluorine, chlorine, bromine, cyano, C₁–C₄-alkyl,    C₁–C₄-halogenoalkyl, C₁–C₄-alkoxy, C₁–C₄-halogenoalkoxy,    C₁–C₄-alkylthio and C₁–C₄-halogenoalkylthio.-   R⁸ and R⁹ furthermore together especially preferably represent    C₂–C₈-alkenylene which is optionally mono- or polysubstituted by    identical or different substituents from the group consisting of    fluorine, chlorine, bromine, C₁–C₄-alkoxy, C₁–C₄-halogenoalkoxy,    C₁–C₄-alkylthio and C₁–C₄-halogenoalkylthio or represent    C₃–C₈-alkylene, which is optionally mono- or polysubstituted in the    alkylene moiety by identical or different substituents from the    group consisting of fluorine, chlorine, cyano, methyl, ethyl,    n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl,    C₁–C₄-halogenoalkyl, methoxy, ethoxy, n-propoxy, isopropoxy,    n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, C₁–C₄-halogenoalkoxy,    methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio,    isobutylthio, sec-butylthio, tert-butylthio and    C₁–C₄-halogenoalkylthio, where the alkylene chain may in each case    be interrupted by —O—, —S— or —NR¹⁸—.-   R¹⁰ and R¹¹ independently of one another especially preferably    represent hydrogen, —SO₂CF₃, methyl, ethyl, n-propyl, isopropyl,    n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, —CF₃,    —CH₂CF₃, —(CF₂)₃CF₃, methoxymethyl, methoxyethyl, cyclopropyl,    cyclopentyl, cyclohexyl, or represent phenyl or benzyl, each of    which is optionally mono- to trisubstituted by identical or    different substituents from the group consisting of fluorine,    chlorine, bromine, methyl, trifluoromethyl, methoxy and    trifluoromethoxy.-   R¹⁰ and R¹¹ furthermore together especially preferably represent    —(CH₂)₄—, —(CH₂)₅—, —(CH₂)₆—, —CH₂—CH(CH₃)—CH₂—CH(CH₃)—CH₂—,    —(CH₂)₂—O—(CH₂)₅—, —(CH₂)₂—S—(CH₂)₂— or —(CH₂)₂—N(R¹⁸)—(CH₂)₂—.-   R¹² and R¹³ independently of one another especially preferably    represent hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl,    isobutyl, sec-butyl, tert-butyl, n-hexyl, trifluoromethyl,    trifluoroethyl, cyclopropyl, cyclopentyl, cyclohexyl or represent    phenyl or benzyl, each of which is optionally mono- to    tetrasubstituted by identical or different substituents from the    group consisting of fluorine, chlorine, bromine, methyl,    trifluoromethyl, methoxy and trifluoromethoxy.-   R¹² and R¹³ furthermore together especially preferably represent    —(CH₂)₃—, —(CH₂)₄—, —(CH₂)₅— or —(CH₂)₆—, each of which is    optionally mono- to tetrasubstituted by identical or different    substituents from the group consisting of fluorine, chlorine,    bromine, methyl, ethyl, methoxy, ethoxy, methylthio, ethylthio,    trifluoromethyl, trifluoromethoxy and trifluoromethylthio.-   R¹⁶ and R¹⁷ independently of one another especially preferably    represent hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl,    isobutyl, sec-butyl, tert-butyl, n-hexyl, trifluoromethyl,    trifluoroethyl, cyclopropyl, cyclopentyl or cyclohexyl.-   R¹⁶ and R¹⁷ furthermore together especially preferably represent    —(CH₂)₃—, —(CH₂)₄—, —(CH₂)₅—, —(CH₂)₂—O—(CH₂)₂— or    —(CH₂)₂—S—(CH₂)₂—.-   R¹⁸ especially preferably represents hydrogen, —SO₂R⁷; represents    —COR⁷ or —CO₂R⁷; represents C₁–C₁₆-alkyl or C₂–C₁₆-alkenyl, each of    which is optionally mono- or polysubstituted by identical or    different substituents from the group consisting of fluorine,    chlorine, bromine, cyano, methylamino, ethylamino,    di-(C₁–C₆-alkyl)amino, C₁–C₄-alkoxy, C₁–C₄-halogenoalkoxy,    C₁–C₄-alkylthio and C₁–C₄-halogenoalkylthio; represents    C₃–C₈-cycloalkyl, cyclopropylmethyl, cyclopentylmethyl,    cyclohexylmethyl, cyclopropylethyl, cyclopentylethyl,    cyclohexylethyl, phenyl, benzyl, phenylethyl, tetrazolyl, furyl,    furfuryl, benzofuryl, tetrahydrofuryl, thienyl, thenyl,    benzothienyl, thiolanyl, pyrrolyl, indolyl, pyrrolinyl,    pyrrolidinyl, oxazolyl, benzoxazolyl, isoxazolyl, imidazolyl,    pyrazolyl, thiazolyl, benzothiazolyl, thiazolidinyl, pyridinyl,    pyrimidinyl, pyridazyl, pyrazinyl, piperidinyl, morpholinyl,    thiomorpholinyl, triazinyl, triazolyl, quinolinyl or isoquinolinyl,    each of which is optionally mono- to trisubstituted by identical or    different substituents from the group consisting of fluorine,    chlorine, bromine, cyano, methyl, ethyl, n-propyl, isopropyl,    n-butyl, isobutyl, sec-butyl, tert-butyl, C₁–C₄-halogenoalkyl,    methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy,    sec-butoxy, tert-butoxy, C₁–C₄-halogenoalkoxy, methylthio,    ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio,    sec-butylthio, tert-butylthio and C₁–C₄-halogenoalkylthio.

Very particular preference is furthermore given to compounds of theformulae (I-1) to (I-16).

in which in each case

-   R¹ represents fluorine r chlorine,-   R² represents hydrogen or fluorine and-   R⁵ has the meanings given above.

In the compounds of the formulae (I-1) to (I-16), R¹, R² and R⁵preferably, particularly preferably, very particularly preferably andespecially preferably have those meanings which have already beenmentioned above as being preferred, particularly preferred, etc., forthese radicals.

Very particular preference is furthermore given to compounds of theformula (I-d) having the (R)-configuration

in which

-   R¹, R², R³ and Het have the meanings given above.

In the compounds of the formula (I-d), R¹, R², R³ and Het preferably,particularly preferably, very particularly preferably and especiallypreferably have those meanings which have already been mentioned aboveas being preferred, particularly preferred, etc., for these radicals.

Very particular preference is furthermore given to compounds of theformulae (I-17) to (I-32) having the (R)-configuration

in which in each case

-   R¹ represents fluorine or chlorine,-   R² represents hydrogen or fluorine and-   R⁵ has the meanings given above.

In the compounds of the formulae (I-17) to (I-32), R¹, R² and R⁵preferably, particularly preferably, very particularly preferably andespecially preferably have those meanings which have already beenmentioned above as being preferred, particularly preferred, etc., forthese radicals.

Compounds of the formula (I-d) are obtained by customary processes foroptical resolution, such as, for example, by chromatographing thecorresponding racemates on a chiral stationary phase. In this manner, itis possible to separate both racemic end products and racemicintermediates into the two enantiomers.

Saturated hydrocarbon radicals, such as alkyl, can in each case bestraight-chain or branched as far as this is possible, including incombination with heteroatoms, such as, for example, an alkoxy.

However, the abovementioned general or preferred radical definitions orillustrations can also be combined with one another as desired, i.e.between the respective ranges and preferred ranges. They apply both tothe end products and, correspondingly, to the precursors andintermediates.

Usingtert-butyl-1-(5-bromo-2-thienyl)-4-(2,6-difluorophenyl)-4-oxobutylcarbamateas starting material and trifluoroacetic acid (TFA), the course of theprocess (A) according to the invention can be illustrated by theequation below.

Using 4-azido-4-(6-chloro-3-pyridinyl)-1-(2,6-difluorophenyl)-1-butanoneas starting material and triphenylphosphine (PPh₃), the course of theprocess (B) according to the invention can be illustrated by theequation below.

UsingN-[1-(4-bromo-2-thienyl)-4-(2,6-difluorophenyl)-4-oxobutyl]acetamide asstarting material and hydrochloric acid (HCl), the course of the process(C) according to the invention can be illustrated by the equation below.

Using2-chloro-5-[5-(2,6-difluorophenyl)-3,4-dihydro-2H-pyrrol-2-yl]pyridineand N-(5-bromo-2-pyrimidinyl)-N,N-diethylamine as starting materials and4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bis-1,3,2-dioxaborolane and apalladium catalyst, the course of the process (D) according to theinvention can be illustrated by the equation below.

Using2-(4,4,5,5′-tetramethyl-1,3,2-dioxaborolan-2-yl)-5-[5-(2,6-difluorophenyl)-3,4-dihydro-2H-pyrrol-2-yl]pyridineand 5-bromo-2-trifluoromethoxypyrimidine as starting materials and apalladium catalyst, the course of the process (E) according to theinvention can be illustrated by the equation below.

Using2-chloro-5-[5-(2,6-difluorophenyl)-3,4-dihydro-2H-pyrrol-2-yl]pyridineand 4-trifluoromethoxyphenylboronic acid as starting materials and apalladium catalyst, the course of the process (F) according to theinvention can be illustrated by the equation below.

Using2-bromo-5-[5-(2,6-difluorophenyl)-3,4-dihydro-2H-pyrrol-2-yl]pyridineand 2-trifluoromethyl-5-(tributylstannyl)pyridine as starting materialsand a palladium catalyst, the course of the process (G) according to theinvention can be illustrated by the equation below.

Explanation of the Processes and IntermediatesProcess (A)

The formula (II) provides a general definition of the aminoketonesrequired as starting materials for carrying out the process (A)according to the invention. In this formula R¹, R², R³ and Hetpreferably, particularly preferably, very particularly preferably andespecially preferably have those meanings which have already beenmentioned in connection with the description of the compounds of theformula (I) according to the invention as being preferred, particularlypreferred, etc., for these radicals.

Aminoketones of the formula (II) are novel. They can be prepared by

-   a) reacting lactams of the formula (IX)

-   -   in which    -   Het has the meanings given above    -   with metallated aromatic compounds of the formula (X)

-   -   in which    -   R¹, R² and R³ have the meanings given above and    -   M¹ represents Li, MgCl, MgBr, MgI or ZnCl,    -   at temperatures between minus 70° C. and plus 70° C., if        appropriate in the presence of a diluent (for example        tetrahydrofuran).

The formula (IX) provides a general definition of the lactams requiredas starting materials for carrying out the process (a). In this formula,Het preferably, particularly preferably, very particularly preferablyand especially preferably has those meanings which have already beenmentioned in connection with the description of the compounds of theformula (I) according to the invention as being preferred, particularlypreferred, etc., for this radical.

Lactams of the formula (IX) are novel. They can be prepared by

-   b) reacting lactams of the formula (XI)

-   -   in which    -   Het has the meanings given above    -   for example with di-tert-butyl dicarbonate in the presence of a        base (for example dimethylaminopyridine) and, if appropriate, in        the presence of a diluent (for example dichloromethane) (cf.        Tetrahedron Lett. 1998, 39, 2705–2706).

The formula (X) provides a general definition of the metallated aromaticcompounds required as starting materials for carrying out the process(a). In this formula, R¹, R² and R³ preferably, particularly preferably,very particularly preferably and especially preferably have thosemeanings which have already been mentioned in connection with thedescription of the compounds of the formula (I) according to theinvention as being preferred, particularly preferred, etc., for theseradicals. M¹ preferably represents Li, MgCl, MgBr, MgI or ZnCl,particularly preferably Li, MgCl, MgBr or MgI, very particularlypreferably Li, MgCl or MgBr.

Metallated aromatic compounds of the formula (X) are known and/or can beprepared by known methods (for example lithiation or Grignard reaction)from the corresponding aromatic or halogenated aromatic compounds.

The formula (XI) provides a general definition of the lactams requiredas starting materials for carrying out the process (b). In this formula,Het preferably, particularly preferably, very particularly preferablyand especially preferably has those meanings which have already beenmentioned in connection with the description of the compounds of theformula (I) according to the invention as being preferred, particularlypreferred, etc., for this radical.

Some of the lactams of the formula (XI) are known. They can be prepared,for example, by

-   c) reacting alkoxylactams of the formula (XII)

-   -   in which    -   R²⁰ represents alkyl    -   either        α) with heteroaromatic compounds of the formula (XIII)        H-Het⁵  (XIII)    -   in which    -   Het⁵ represents 5- to 14-membered heteroaryl which comprises 1        to 3 aromatic rings and one or more heteroatoms from the group        consisting of oxygen and sulphur and is optionally mono- to        tetrasubstituted by identical or different R⁵, where R⁵ has the        meanings given above,    -   in the presence of a protonic acid (for example sulphuric acid,        acetic acid) or a Lewis acid (for example-aluminium chloride),        if appropriate in the presence of a diluent (for example        dichloromethane or acetonitrile) (cf. Tetrahedron 1976, 32,        1571),        or

-   β) with Grignard compounds of the formula (XIV)

-   -   in which    -   Het has the meanings given above and    -   Hal¹ represents halogen    -   in the presence of a diluent (for example tetrahydrofuran) (cf.        Org. Prep. Proced. Int. 1993, 25, 255).

The formula (XII) provides a general definition of the alkoxylactamsrequired as starting materials for carrying out the process (c). In thisformula, R²⁰ preferably represents C₁–C₆-alkyl, particularly preferablyC₁–C₄-alkyl, very particularly preferably methyl or ethyl.

The alkoxylactams of the formula (XII) are known and can be prepared,for example, from the corresponding unsubstituted imides by cathodicreduction or reduction with sodium boronate or from the unsubstitutedlactams by anodic oxidation (cf. J. Org. Chem. 1991, 56, 1822; Synthesis1980, 315).

The formula (XIII) provides a general definition of the heteroaromaticcompounds required as starting materials for carrying out the process(α). In this formula, Het⁵ preferably represents 5- to 14-memberedheteroaryl which comprises 1 to 3 aromatic rings and 1 or 2 heteroatomsincluding 0 to 2 nonadjacent oxygen atoms and/or 0 to 2 nonadjacentsulphur atoms (in particular thienyl, benzothienyl, furyl, benzofuryl,thienothienyl, thienofuryl, thienobenzothienyl or thienobenzofuryl),each of which radicals is optionally mono- to tetrasubstituted byidentical or different R⁵. Het⁵ particularly preferably represents2-thienyl, 3-thienyl, 2-benzo[b]thienyl, 2-furyl, 3-furyl,2-benzo[b]furyl, 2-thieno[3,2-b]thienyl, 2-thieno[3,2-b]furyl,5-thieno[3,2--b]furyl, 2-thieno[2,3-f][1]benzothienyl,2-thieno[2,3-f][1]benzofuryl or 6-thieno[2,3-f][1]benzofuryl, each ofwhich is optionally mono- to trisubstituted by identical or differentR⁵. Het⁵ very particularly preferably represents 2-thienyl, 3-thienyl,2-benzo[b]thienyl, 2-furyl, 3-furyl, 2-benzo[b]furyl,2-thieno[3,2-b]thienyl, 2-thieno[3,2-b]furyl, 5-thieno[3,2-b]furyl,2-thieno[2,3-f][1]benzothienyl, 2-thieno[2,3-f][)]benzofuryl or6-thieno[2,3-f][1]benzofuryl, each of which is optionally mono- ordisubstituted by identical or different R⁵. R⁵ here preferably,particularly preferably, very particularly preferably and especiallypreferably has those meanings which have already been mentioned inconnection with the description of the compounds of the formula (I)according to the invention as being preferred, particularly preferred,etc., for these radicals.

The heteroaromatic compounds of the formula (XIII) are known and/or canbe prepared by known methods.

The formula (XIV) provides a general definition of the Grignardcompounds required as starting materials for carrying out the process(β). In this formula, Het preferably, particularly preferably, veryparticularly preferably and especially preferably has those meaningswhich have already been mentioned in connection with the description ofthe compounds of the formula (I) according to the invention as beingpreferred, particularly preferred, etc., for this radical. Hallpreferably represents chlorine, bromine or iodine.

The Grignard compounds of the formula (XIV) are known and/or can beprepared by known processes.

Suitable diluents for carrying out the process (A) according to theinvention are in each case all customary inert organic solvents.Preference is given to using optionally halogenated aliphatic, alicyclicor aromatic hydrocarbons, such as petroleum ether, hexane, heptane,cyclohexane, methylcyclohexane, benzene, toluene, xylene or decaline;chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbontetrachloride, dichloroethane or trichloroethane; ethers, such asdiethyl ether, diisopropyl ether, methyl tert-butyl ether, methyltert-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane,1,2-diethoxyethane or anisole; nitriles, such as acetonitrile,propionitrile, n- or isobutyronitrile or benzonitrile; amides, such asN,N-dimethylformamide, N,N-dimethylacetamide, N-methylformanilide,N-methylpyrrolidone or hexamethylphosphoric triamide; esters, such asmethyl acetate or ethyl acetate; sulphoxides, such as dimethylsulphoxide; or sulphones, such as sulpholane. Methylene chloride,chloroform, toluene, methanol or ethanol are used with particularpreference.

Suitable for carrying out the process (A) according to the invention arein each case all customary Lewis acids or protonic acids. Methods forremoving Boc are generally known (cf., for example, T. W. Greene, P. G.M. Wuts, Protective Groups in Organic Synthesis, Ed. 3, New York, Wiley& Sons, 1999, pp. 520–525). Preference is given to using trifluoroaceticacid, HCl or HBr for removing the Boc protective group.

When carrying out the process (A) according to the invention, thereaction temperatures can in each case be varied within a relativelywide range. In general, the process is carried out at temperaturesbetween −20° C. and +120° C., preferably between −10° C. and 60° C.

When carrying out the process (A) according to the invention, in general100 mol of a protonic acid are employed per mole of the compounds of theformula (II).

However, it is also possible to employ the reaction components in otherratios. Work-up is carried out by customary methods. In general, thereaction mixture is concentrated, taken up in a suitable solvent andadjusted to pH 12 using sodium hydroxide, and the organic phase iswashed with water, dried over sodium sulphate, filtered andconcentrated. The residue is, if appropriate, freed from any impuritiesthat may still be present using customary methods, such aschromatography or recrystallization.

Process (B)

The formula (III) provides a general definition of the azides requiredas starting materials for carrying out the process (B) according to theinvention. In this formula R¹, R², R³ and Het preferably, particularlypreferably, very particularly preferably and especially preferably havethose meanings which have already been mentioned in connection with thedescription of the compounds of the formula (I) as being preferred,particularly preferred, etc., for these radicals.

Azides of the formula (III) are novel. They can be prepared by

-   d) reacting halides of the formula (XV)

-   -   in which    -   R¹, R², R³ and Het have the meanings given above and    -   Hal² represents halogen    -   with azides of the formula (XVI)        Q-N₃  (XVI)    -   in which    -   Q represents a cation    -   in the presence of a diluent (for example water/acetone mixtures        or water/ethanol mixtures) and, if appropriate, in the presence        of a catalyst (for example methyltrioctylammonium        chloride=Aliquat 336, cf. M. Es-Sayed, Phd Thesis, University of        Göttingen, 1992).

The formula (XV) provides a general definition of the halides requiredas starting materials for carrying out the process (d). In this formulaR¹, R², R³ and Het preferably, particularly preferably, veryparticularly preferably and especially preferably have those meaningswhich have already been mentioned in connection with the description ofthe compounds of the formula (I) according to the invention as beingpreferred, particularly preferred, etc., for these radicals. Hal²preferably represents chlorine, bromine or iodine, particularlypreferably chlorine or bromine, very particularly preferably chlorine.

Halides of the formula (XV) are novel. They can be prepared by

-   e) reacting cyclopropanes of the formula (XVII)

-   -   in which    -   R¹, R², R³ and Het have the meanings given above    -   with a protonic acid (for example HCl), if appropriate in the        presence of a diluent (for example water).

The formula (XVI) provides a general definition of the azides requiredas starting materials for carrying out the process (d). In this formula,Q preferably represents alkali metal ions, trialkylsilyl,tetraalkylammonium, tetraalkylguanidinium or polymer-boundtrialkylammonium. With particular preference, Q represents sodium,lithium, trimethylsilyl, tetraethylammonium, tetra-n-butylammonium ortetramethylguanidinium, very particularly preferably sodium or lithium.

Azides of the formula (XVI) are commercially available and/or can beprepared by known methods (cf. Houben-Weyl: Methoden der OrganischenChemie, 4. edition, Organonitrogen Compounds I, pages 1243–1290; Editor:D. Klamann).

The formula (XVII) provides a general definition of the cyclopropanesrequired as starting materials for carrying out the process (e). In thisformula R¹, R², R³ and Het preferably, particularly preferably, veryparticularly preferably and especially preferably have those meaningswhich have already been mentioned in connection with the description ofthe compounds of the formula (I) as being preferred, particularlypreferred, etc., for these radicals.

Some of the cyclopropanes of the formula (XVII) are known. They can beprepared, for example, by

-   f) reacting α,β-unsaturated ketones of the formula (XVIII)

-   -   in which    -   R¹, R², R³ and Het have the meanings given above    -   with a trialkylsulphoxonium halide (for example        trimethylsulphoxonium iodide) in the presence of a base (for        example sodium hydride) and, if appropriate, in the presence of        a diluent (for example dimethyl sulphoxide) (cf. Tetrahedron        Asymmetry 1998, 9, 1035).

The formula (XVIII) provides a general definition of the α,β-unsaturatedketones required as starting materials for carrying out the process (f).In this formula R¹, R², R³ and Het preferably, particularly preferably,very particularly preferably and especially preferably have thosemeanings which have already been mentioned in connection with thedescription of the compounds of the formula (I) according to theinvention as being preferred, particularly preferred, etc., for theseradicals.

α,β-Unsaturated ketones of the formula (XVIII) are known. They can beprepared, for example, by

-   g) reacting aldehydes of the formula (XIX)    Het-CHO  (XIX)    -   in which    -   Het has the meanings given above    -   with acetophenones of the formula (XX)

-   -   in which    -   R¹, R² and R³ have the meanings given above    -   in the presence of a base (for example sodium hydroxide) and in        the presence of a diluent (for example methanol).

The formula (XIX) provides a general definition of the aldehydesrequired as starting materials for carrying out the process (g). In thisformula, Het preferably, particularly preferably, very particularlypreferably and especially preferably has those meanings which havealready been mentioned in connection with the description of thecompounds of the formula (I) according to the invention as beingpreferred, particularly preferred, etc., for these radicals.

Aldehydes of the formula (XIX) are known and/or can be prepared by knownmethods.

The formula (XX) provides a general definition of the acetophenonesrequired as starting materials for carrying out the process (g). In thisformula R¹, R² and R³ preferably, particularly preferably, veryparticularly preferably and especially preferably have those meaningswhich have already been mentioned in connection with the description ofthe compounds of the formula (I) according to the, invention as beingpreferred, particularly preferred, etc., for these radicals.

Acetophenones of the formula (XX) are known and/or can be prepared byknown methods.

-   Cyclopropanes of the formula (XVII-a)

in which

-   R¹, R², R³ and Het¹ have the meanings given above    -   can also be prepared by-   h) reacting cyclopropanes of the formula (XVII-b)

-   -   in which    -   R¹, R², R³ and Het² have the meanings given above with boronic        acid derivatives of the formula (VII)        A²-Y¹-E  (VII)    -   in which    -   Y¹, E and A² have the meanings given above    -   in the presence of a catalyst, if appropriate in the presence of        an acid binder and, if appropriate, in the presence of a        diluent.

This process corresponds to the process (F) according to the inventionin which Δ¹-pyrrolines of the formula (I-b) are reacted. The couplingreactions according to processes (D) and (E) can also be applied tocyclopropanes of the formula (XVII-a).

The cyclopropanes of the formula (XVII-b) used as starting materials inprocess (h) are a sub-group of the compounds of the formula (XVII) andcan be prepared analogously to process (f).

Boronic acid derivatives of the formula (VII) are described below in thedescription of process (F) according to the invention.

For process (h), it is possible to use the same reaction conditions,diluents, reaction auxiliaries and catalysts as for process (F)described below.

When carrying out the process (B) according to the invention, it ispossible to employ all the trialkylphosphines, triarylphosphines andtrialkyl phosphites which are customarily used for this purpose (cf.Tetrahedron Lett. 1999, 40, 4825; Tetrahedron 1997, 53, 3693;Tetrahedron 1997, 55, 8353; J. Chem. Soc. Chem. Commun. 1982, 1224;Synthesis 1996, 123). Preference is given to using organophosphoruscompounds such as triphenylphosphine, tri-n-butylphosphine or trimethylphosphite, particularly preferably triphenylphosphine.

It is furthermore possible to convert azides of the formula (III) bycatalytic hydrogenation, for example with the catalyst PtO₂, accordingto the process according to the invention and compounds of the formula(I) (cf. J. Am. Chem. Soc. 1954, 76, 1231).

Further alternatives for reducing azido compounds are described in theliterature (cf. Houben-Weyl: Methoden der Organischen Chemie, 4.Edition, Organonitrogen Compounds II, pages 956–975; Editor: D.Klamann).

Suitable diluents for carrying out the process (B) according to theinvention are aliphatic or aromatic hydrocarbons, halogenatedhydrocarbons or ethers. Preference is given to using pentane, hexane,heptane, benzene, toluene, tetrahydrofuran, diethyl ether, dioxane oracetonitrile, particularly preferably pentane, hexane or heptane.

The reaction temperatures for carrying out the process (B) according tothe invention can be varied within a relatively wide range. In general,the process is carried out at temperatures between −10° C. and +60° C.,preferably between 0° C. and 40° C., particularly preferably at roomtemperature.

When carrying out the process (B) according to the invention, in general1 mol of trialkylphosphine or triarylphosphine or trialkyl phosphite anda suitable diluent are employed per mole of the azide of the formula(III). However, it is also possible to choose other ratios of thereaction components. Work-up is carried out by customary methods. Ingeneral, the reaction mixture is concentrated in the presence ofFlorisil and then chromatographed using a mixture of n-hexane and ethylacetate.

Process (C)

The formula (IV) provides a general definition of the amides required asstarting materials for carrying out the process (C) according to theinvention. In this formula R¹, R², R³ and Het preferably, particularlypreferably very particularly preferably and especially preferably havethose meanings which have already been mentioned in connection with thedescription of the compounds of the formula (I) according to theinvention as being preferred, particularly preferred, etc., for theseradicals. R¹⁹ preferably represents C₁–C₄-alkyl, C₁–C₄-halogenoalkyl,phenyl or arylalkyl, particularly preferably methyl, ethyl, phenyl orbenzyl, very particularly preferably methyl, phenyl or benzyl.

Amides of the formula (IV) are novel. They can be prepared by

-   i) reacting cyclopropanes of the formula (XVII)

-   -   in which    -   R¹, R², R³ and Het have the meanings given above    -   with a nitrile of the formula (XXI)        R¹⁹—CN  (XXI)    -   in which    -   R¹⁹ has the meanings given above    -   in the presence of a protonic acid (for example sulphuric acid)        if appropriate in the presence of a diluent.

The cyclopropanes of the formula (XVII) required as starting materialsfor carrying out the process (i) have already been described inconnection with the explanation of the process (B) according to theinvention.

The formula (XXI) provides a general definition of the nitriles requiredas starting materials for carrying out the process (i). In this formula,R¹⁹ preferably, particularly preferably, very particularly preferablyand especially preferably has those meanings which have already beenmentioned in connection with the description of the compounds of theformula (IV) as being preferred, particularly preferred, etc. for theseradicals.

When carrying out the process (C) according to the invention, protonicacids (cf. J. Org. Chem. 1978, 43, 4593), inorganic bases (cf. J. Chem.Soc. 1964, 4142), hydrazines (cf. J. Org. Chem. 1978, 43, 3711) orbiotransformations with enzymes (cf. Appl. Microbiol. Biotechnol. 1997,47, 650) are used for N-deacylating the amides of the formula (IV)during the conversion into pyrrolines of the formula (I). Othercustomary processes for deacetylating amides have been described in T.W. Greene, P. G. M. Wuts, Protective Groups in Organic Synthesis (Ed. 3,New York, Wiley 1999, pp. 553–555).

Preferred N-deacetylating agents are protonic acids or organic acids,particularly preferably aqueous hydrochloric acid, aqueous hydrobromicacid or trifluoroacetic acid, very particularly preferably aqueoushydrochloric acid; preferably inorganic bases, particularly preferablybarium hydroxide [Ba(OH)₂] and sodium hydroxide (NaOH) and preferablybiotransformations, particularly preferably with the use of acylases.

If the N-deacylation is carried out using biotransformations, thecompounds of the formula (I) are obtained in a form where one of the twoenantiomers is present in excess.

Suitable diluents for carrying out the process (C) according to theinvention are water or alcohols and mixtures of these. Preference isgiven to using water, methanol or ethanol or mixtures of two or three ofthese three diluents.

When carrying out the process (C) according to the invention, thereaction temperatures can be varied within a relatively wide range. Ingeneral, the process is carried out at temperatures between 20° C. and200° C., preferably between 60° C. and 140° C., particularly preferablybetween 80° C. and 120° C. If the N-deacylation is carried outenzymatically using acylases, the process is generally carried out attemperatures between 20° C. and 60° C., preferably between 20° C. and40° C.

When carrying out the process (C) according to the invention, in general2 parts by volume of a protonic acid are employed per part by volume ofa 10% strength (w/v) alcoholic solution of the amide of the formula(IV). However, it is also possible to choose other ratios of thereaction components. Work-up is carried out by customary methods. Ingeneral, the reaction mixture is neutralized with aqueous sodiumhydroxide solution and then extracted with ethyl acetate and the organicphase is dried, filtered and concentrated.

Process (D)

In a first reaction step, a compound of the formula (I-b) is coupledwith a diboronic acid ester in the presence of a palladium catalyst, ifappropriate in the presence of an acid binder and if appropriate in thepresence of a solvent. Without any isolation of the intermediate, acompound of the formula (V) is coupled in the same reaction vessel in asecond reaction step in the presence of a catalyst, if appropriate inthe presence of an acid binder and if appropriate in the presence of asolvent (cf., for example, Tetrahedron Lett. 1997, 38, 3841).

The process (D) according to the invention can be carried out in twovariants. It is possible either to initially charge a compound of theformula (I-b) or to initially charge a compound of the formula (V).Process (D) is to be considered a tandem reaction of the processes E)and (F) described below.

The formula (I-b) provides a general definition of the Δ¹-pyrrolinesrequired as starting materials for carrying out the process (D)according to the invention. In this formula R¹, R² and R³ preferably,particularly preferably, very particularly preferably and especiallypreferably have those meanings which have already been mentioned inconnection with the description of the compounds of the formula (I)according to the invention as being preferred, particularly preferred,etc., for these radicals. Het² preferably represents 5- to 14-memberedheteroaryl which comprises 1 to 3 aromatic rings and one or moreheteroatoms from the group consisting of nitrogen, oxygen and sulphurand which is monosubstituted by R⁵⁻². Het² particularly preferablyrepresents 5- to 14-membered heteroaryl which comprises 1 to 3 aromaticrings and 1 to 4 heteroatoms including 0 to 4 nitrogen atoms, 0 to 2nonadjacent oxygen atoms and/or 0 to 2 nonadjacent sulphur atoms (inparticular thienyl, benzothienyl, furyl, benzofuryl, indolyl,thienothienyl, thienofuryl, thienobenzothienyl, thienobenzofuryl,pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazolyl or tetrazolyl)which is monosubstituted by R⁵⁻². Het² very particularly preferablyrepresents 2-thienyl, 3-thienyl, 2-benzo[b]thienyl, 2-furyl, 3-furyl,2-benzo[b]furyl, 2-indolyl, 2-thieno[3,2-b]thienyl,2-thieno[3,2-b]furyl, 5-thieno[3,2-b]furyl,2-thieno[2,3-f][1]benzothienyl, 2-thieno[2,3-f][1]benzofuryl,6-thieno[2,3-f][1]benzofuryl, 2-pyridinyl, 3-pyridinyl, 2-pyrimidinyl,5-pyrimidinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrazinyl, triazolyl ortetrazolyl which is monosubstituted by R⁵⁻². Het² especially preferablyrepresents 2-thienyl, 3-thienyl, 2-benzo[b]thienyl, 2-furyl, 3-furyl,2-benzo[b]furyl, 2-thieno[3,2-b]thienyl, 2-thieno[3,2-b]furyl,5-thieno[3,2-b]furyl, 2-thieno[2,3-f][1]benzothienyl,2-thieno[2,3-f][1]benzofuryl, 6-thieno[2,3-f][1]benzofuryl, 2-pyridinyl,3-pyridinyl, 2-pyrimidinyl, 5-pyrimidinyl, 3-pyridazinyl, 4-pyridazinylor 2-pyrazinyl which is monosubstituted by R⁵⁻². R⁵⁻² preferablyrepresents bromine, iodine —OSO₂CF₃ or —OSO₂(CF₂)₃CF₃, particularlypreferably bromine, —OSO₂CF₃ or —OSO₂(CF₂)₃, very particularlypreferably bromine or —OSO₂CF₃.

Δ¹-Pyrrolines of the formula (I-b) form part of the subject-matter ofthe present invention and can be prepared by one of the processes (A),(B) or (C).

The formula (V) provides a general definition of the heterocyclesrequired as starting materials for carrying out the process (D)according to the invention. In this formula E preferably, particularlypreferably, very particularly preferably and especially preferably hasthose meanings which have already been mentioned in connection with thedescription of the compounds of the formula (I) according to theinvention as being preferred, particularly preferred, etc., for theseradicals. Y¹ preferably represents phenylene or 5- to 10-memberedsaturated or unsaturated heterocyclylene having one or more heteroatomsfrom the group consisting of nitrogen, oxygen and sulphur, each of whichradicals is optionally mono- to tetrasubstituted by identical ordifferent radicals from the list W¹. Y¹ particularly preferablyrepresents 1,4-phenylene, 1,3-phenylene or 1,2-phenylene, each of whichis optionally mono- to tetrasubstituted by identical or differentradicals from the list W¹; or represents 5- to 6-membered saturated orunsaturated heterocyclylene having 1 to 3 heteroatoms including 0 to 3nitrogen atoms, 0 to 2 nonadjacent oxygen atoms and 0 to 2 nonadjacentsulphur atoms (in particular furylene, thienylene, pyrrolylene,oxazolylene, thiazolylene, pyridinylene, pyrimidinylene, pyridazinyleneor pyrazinylene), each of which radicals is optionally mono- totetrasubstituted by identical or different radicals from the list W¹. Y¹very particularly preferably represents 1,4-phenylene, 1,3-phenylene,1,2-phenylene, 2,4-furylene, 2,4-thienylene, 2,4-pyrrolylene,2,5-oxazolylene, 2,5-thiazolylene, 2,5-pyridinylene, 2,6-pyridinylene,2,5-pyrimidinylene, 3,6-pyridazinylene or 2,5-pyrazinylene each of whichis optionally mono- to trisubstituted by identical or different radicalsfrom the list W¹. Y¹ especially preferably represents 1,4-phenylene,1,3-phenylene, 2,4-furylene, 2,4-thienylene, 2,5-pyridinylene,2,5-pyrimidinylene, 3,6-pyridazinylene or 2,5-pyrazinylene each of whichis optionally mono- or disubstituted by identical or different radicalsfrom the list W¹. W¹ preferably, particularly preferably, veryparticularly preferably and especially preferably has those meaningswhich have already been mentioned in connection with the description ofthe compounds of the formula (I) according to the invention as beingpreferred, particularly preferred, etc., for these radicals. A¹preferably represents bromine, chlorine, iodine or —OSO₂CF₃ particularlypreferably bromine, chlorine or iodine, very particularly preferablybromine or chlorine.

The heterocycles of the formula (V) are known or can be prepared byknown processes (cf. Aust. J. Chem. 1964, 17, 794; Chem. Ber. 1992, 125,1169; Chem. Pharm. Bull. 1995, 43, 247; Eur. J. Med. Chem. 1989, 24,249; J. Chem. Soc. C 1971, 1889; J. Chem. Soc. Perkin Trans. 1 1995,2497; J. Med. Chem. 1991, 34, 315; J. Org. Chem. 1984, 49, 2240; J. Org.Chem. 1990, 55, 69; Org. Prep. Proced. Int. 1998, 30, 433; Synthesis1999, 1163; Tetrahedron 1999, 40, 7975; Tetrahedron Lett. 1996, 37,4447; Tetrahedron Lett. 2000, 41, 4335).

Suitable diboronic acid esters for carrying out the process (D)according to the invention are4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bis-1,3,2-dioxaborolane,5,5,5′,5′-tetramethyl-2,2′-bis-1,3,2-dioxaborinane,4,4,4′,4′,6,6′-hexamethyl-2,2′-bis-1,3,2-dioxaborinane or2,2′-bis-1,3,2-benzodioxaborole. Preference is given to using4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bis-1,3,2-dioxaborolane,5,5,5′,5′-tetramethyl-2,2′-bis-1,3,2-dioxaborinane or4,4,4′,4′,6,6′-hexamethyl-2,2′-bis-1,3,2-dioxaborinane, particularlypreferably 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bis-1,3,2-dioxaborolaneor 5,5,5′,5′-tetramethyl-2,2′-bis-1,3,2-dioxaborinane, very particularlypreferably 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bis-1,3,2-dioxaborolane.

When carrying out the process (D) according to the invention, in general1 mol or a slight excess of a diboronic ester and 1 mol or a slightexcess of a compound of the formula (V), and 3% of a palladium catalyst,are employed per mole of the compound of the formula (I-b). However, itis also possible to employ the reaction components in other ratios. Itis possible to initially charge the compound of the formula (I-b) or,alternatively, the compound of the formula (V). Work-up is carried outby customary methods. In general, the reaction, mixture is diluted withwater and extracted with ethyl acetate. The organic phase is washed,dried, filtered and concentrated. The residue is, if appropriate, freedfrom any impurities that may still be present using customary methods,such as chromatography or recrystallization.

Process (E)

The formula (VI) provides a general definition of the Δ¹-pyrrolinesrequired as starting materials for carrying out the process (E)according to the invention. In this formula R¹, R² and R³ preferably,particularly preferably, very particularly preferably and especiallypreferably have those meanings which have already been mentioned inconnection with the description of the compounds of the formula (I) asbeing preferred, particularly preferred etc., for these radicals. Het³preferably represents 5- to 14-membered heteroaryl which comprises 1 to3 aromatic rings and one or more heteroatoms from the group consistingof nitrogen, oxygen and sulphur and is monosubstituted by A². Het³particularly preferably represents 5- to 14-membered heteroaryl whichcomprises 1 to 3 aromatic rings and 1 to 4 heteroatoms including 0 to 4nitrogen atoms, 0 to 2 nonadjacent oxygen atoms and/or 0 to 2nonadjacent sulphur atoms (in particular thienyl, benzothienyl, furyl,benzofuryl, indolyl, thienothienyl, thienofuryl, thienobenzothienyl,thienobenzofuryl, pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl,triazolyl or tetrazolyl), which radicals are monosubstituted by A². Het³very particularly preferably represents 2-thienyl, 3-thienyl,2-benzo[b]thienyl, 2-furyl, 3-furyl, 2-benzo[b]furyl, 2-indolyl,2-thieno[3,2b]thienyl, 2-thieno[3,2-b]furyl, 5-thieno[3,2-b]furyl,2-thieno[2,3-f][1]benzothienyl, 2-thieno[2,3-f][1]benzofuryl,6-thieno[2,3-f][1]benzofuryl, 2-pyridinyl, 3-pyridinyl, 2-pyrimidinyl,5-pyrimidinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrazinyl, triazolyl ortetrazolyl which is monosubstituted by A². Het³ especially preferablyrepresents 2-thienyl, 3-thienyl, 2-benzo[b]thienyl, 2-furyl, 3-furyl,2-benzo[b]furyl, 2-thieno[3,2-b]thienyl, 2-thieno[3,2-b]furyl,5-thieno[3,2-b]furyl, 2-thieno[2,3-f][1]benzothienyl,2-thieno[2,3-f][1]benzofuryl, 6-thieno[2,3-f][1]benzofuryl, 2-pyridinyl,3-pyridinyl, 2-pyrimidinyl, 5-pyrimidinyl, 3-pyridazinyl, 4-pyridazinylor 2-pyrazinyl which is monosubstituted by A². A² preferably represents—B(OH)₂, (4,4,5,5-tetramethyl-1,3,2-dioxaborolan)-2-yl,(5,5-dimethyl-1,3,2-dioxaborinan)-2-yl,(4,4,6-trimethyl-1,3,2-dioxaborinan)-2-yl or 1,3,2-benzodioxaborol-2-yl,particularly preferably —B(OH)₂,(4,4,5,5-tetramethyl-1,3,2-dioxaborolan)-2-yl,(5,5-dimethyl-1,3,2-dioxaborinan)-2-yl or(4,4,6-trimethyl-1,3,2-dioxaborinan)-2-yl, very particularly preferably—B(OH)₂, (4,4,5,5-tetramethyl-1,3,2-dioxaborolan)-2-yl,(5,5-dimethyl-1,3,2-dioxaborinan)-2-yl.

Δ¹-Pyrrolines of the formula (VI) can be prepared by

-   k) reacting compounds of the formula (I-b)

-   -   in which    -   R¹, R², R³ and Het² have the meanings given above,    -   with a diboronic acid ester in the presence of a catalyst, if        appropriate in the presence of an acid binder and if appropriate        in the presence of a diluent (cf. J. Org. Chem. 1995, 60, 7508;        Tetrahedron Lett. 1997, 38, 3447).

Diboronic acid esters suitable for carrying out the process (k) havealready been mentioned in the description of the process (D) accordingto the invention.

The heterocycles of the formula (V) required as starting materials forcarrying out the process (E) according to the invention have alreadybeen described above in the description of the process (D).

When carrying out the process (E) according to the invention, in general1 mol or a slight excess of a compound of the formula (V) is employedper mole of the compound of the formula (VI). However, it is alsopossible to employ the reaction components in other ratios. Work-up iscarried out by customary methods. In general, the reaction mixture istaken up in ethyl acetate and the organic phase is washed with water,dried over sodium sulphate, filtered and concentrated. The residue is,if appropriate, freed from any impurities that may still be presentusing customary methods, such as chromatography or recrystallization.

Process (F)

The Δ¹-pyrrolines of the formula (I-b) required as starting materialsfor carrying out the process (F) according to the invention have alreadybeen described in the description of the process (D).

The formula (VII) provides a general definition of the boronic acidderivatives required as starting materials for carrying out the process(F) according to the invention. In this formula, E preferably,particularly preferably, very particularly preferably and especiallypreferably has those meanings which have already been mentioned inconnection with the description of the compounds of the formula (I)according to the invention as being preferred, particularly preferred,etc., for these radicals. Y¹ preferably, particularly preferably, veryparticularly preferably and especially preferably has those meaningswhich have already been mentioned in connection with the description ofthe compounds of the formula (V) as being preferred, particularlypreferred, etc., for these radicals. A² preferably, particularlypreferably, very particularly preferably and especially preferably hasthose meanings which have already been mentioned in connection with thedescription of the compounds of the formula (VI) as being preferred,particularly preferred, etc., for these radicals.

The compounds of the formula (VII) are known or can be prepared by knownprocesses (cf. J. Org. Chem. 1995, 60, 7508, Tetrahedron Lett. 1997, 38,3447).

When carrying out the process (F) according to the invention, in general1 mol or a slight excess of a compound of the formula (VII) is employedper mole of the compound of the formula (I-b). However, it is alsopossible to employ the reaction components in other ratios. Work-up iscarried out by customary methods. In general, the reaction mixture istaken up in ethyl acetate and the organic phase is washed with water,dried over sodium sulphate, filtered and concentrated. The residue is,if appropriate, freed from any impurities that may still be presentusing customary methods, such as chromatography or recrystallization.

Process (G)

The formula (I-c) provides a general definition of the Δ¹-pyrrolinesrequired as starting materials for carrying out the process (G)according to the invention. In this formula R¹, R² and R³ preferably,particularly preferably, very particularly preferably and especiallypreferably have those meanings which have already been mentioned inconnection with the description of the compounds of the formula (I)according to the invention as being preferred, particularly preferred,etc., for these radicals. Het⁴ preferably represents 5- to 14-memberedheteroaryl which comprises 1 to 3 aromatic rings and one or moreheteroatoms from the group consisting of nitrogen, oxygen and sulphurand is substituted by R⁵⁻³. Het⁴ particularly preferably represents 5-to 14-membered heteroaryl having 1 to 4 heteroatoms including 0 to 4nitrogen atoms, 0 to 2 nonadjacent oxygen atoms and/or 0 to 2nonadjacent sulphur atoms (in particular thienyl, benzothienyl, furyl,benzofuryl, indolyl, thienothienyl, thienofuryl, thienobenzothienyl,thienobenzofuryl, pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl,triazolyl or tetrazolyl), which radicals are monosubstituted by R⁵⁻³.Het⁴ very particularly preferably represents 2-thienyl, 3-thienyl,2-benzo[b]thienyl, 2-indolyl, 2-furyl, 3-furyl, 2-benzo[b]furyl,2-thieno[3,2-b]thienyl, 2-thieno[3,2-b]furyl, 5-thieno[3,2-b]furyl,2-thieno[2,3-f][1]benzothienyl, 2-thieno[2,3-f][1]benzofuryl,6-thieno[2,3-f][1]benzofuryl, 2-pyridinyl, 3-pyridinyl, 2-pyrimidinyl,5-pyrimidinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrazinyl, triazolyl ortetrazolyl which is monosubstituted by R⁵⁻³. Het⁴ especially preferablyrepresents 2-thienyl, 3-thienyl, 2-benzo[b]-thienyl, 2-furyl, 3-furyl,2-benzo[b]furyl, 2-thieno[3,2-b]thienyl, 2-thieno[3,2-b]furyl,5-thieno[3,2-b]furyl, 2-thieno[2,3-f][1]benzothienyl,2-thieno[2,3-f][1]benzofuryl, 6-thieno[2,3-f][1]benzofuryl, 2-pyridinyl,3-pyridinyl, 2-pyrimidinyl, 5-pyrimidinyl, 3-pyridazinyl, 4-pyridazinylor 2-pyrazinyl which is monosubstituted by R⁵⁻³. R⁵⁻³ preferablyrepresents bromine or iodine.

Δ¹-Pyrrolines of the formula (I-c) form part of the subject-matter ofthis invention and can be prepared by one of the processes (A), (B) or(C).

The formula (VIII) provides a general definition of the organometalliccompounds required as starting materials for carrying out the process(G) according to the invention. In this formula, E preferably,particularly preferably, very particularly preferably and especiallypreferably has those meanings which have already been mentioned inconnection with the description of the compounds of the formula (I)according to the invention as being preferred, particularly preferred,etc., for these radicals. In this formula, Y¹ preferably, particularlypreferably, very particularly preferably and especially preferably hasthose meanings which have already been mentioned in connection with thedescription of the compounds of the formula (V) as being preferred,particularly preferred, etc., for these radicals. M preferablyrepresents ZnCl, Sn(Me)₃ or Sn(n-Bu)₃.

Some of the organometallic compounds of the formula (VIII) are known,and/or they can be prepared by known methods. It is possible, forexample, to prepare compounds of the formula (VIII) in situ from thecorresponding compounds of the formula (V) in which A¹ represents—OSO₂CF₃ (cf. Tetrahedron Lett. 1995, 36, 9085).

When carrying out the process (G) according to the invention, in general1 mol or a slight excess of a compound of the formula (VIII) is employedper mole of the compound of the formula (I-c). However, it is alsopossible to employ the reaction components in other ratios. Work-up iscarried out by customary methods. In general, the reaction mixture istaken up in ethyl acetate and the organic phase is washed with water,dried over sodium sulphate, filtered and concentrated. The residue is,if appropriate, freed from any impurities that may still be presentusing customary methods, such as chromatography or recrystallization.

When carrying out the processes (D), (E), (F) and (G) according to theinvention, in each case a palladium catalyst is employed, which for itspart can be used with or without addition of further ligands. Thecatalyst used is preferably PdCl₂(dppf)[dppf=1,1′-bis(diphenylphosphino)ferrocene], Pd(PPh₃)₄, PdCl₂(PPh₃)₂,PdCl₂(CH₃CN)₂, Pd₂(dba)₃ [dba=dibenzylideneacetone] or Pd(OAc)₂,particularly preferably PdCl₂(dppf), Pd(PPh₃)₄, PdCl₂(PPh₃)₂, orPd(OAc)₂, very particularly preferably PdCl₂(dppf) or PdCl₂(PPh₃)₂.

Suitable ligands are triarylphosphines; trialkylphosphines or arsines.Preference is given to using dppf, PPh₃, P(t-Bu)₃, Pcy₃ or AsPh₃,particularly preferably dppf.

Suitable diluents for carrying out the processes (D), (E) and (F)according to the invention are in each case all customary inert organicsolvents. Preference is given to using optionally halogenated aliphatic,alicyclic or aromatic hydrocarbons, such as petroleum ether, hexane,heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene ordecaline; chlorobenzene, dichlorobenzene, dichloromethane, chloroform,carbon tetrachloride, dichloroethane or trichloroethane; ethers, such asdiethyl ether, diisopropyl ether, methyl tert-butyl ether, methyltert-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane,1,2-diethoxyethane or anisole; nitriles, such as acetonitrile,propionitrile, n- or isobutyronitrile or benzonitrile; amides, such asN,N-dimethylformamide, N,N-dimethylacetamide, N-methylformanilide,N-methylpyrrolidone or hexamethylphosphoric triamide; esters, such asmethyl acetate or ethyl acetate; sulphoxides, such as dimethylsulphoxide or sulphones, such as sulpholane. Particular preference isgiven to using acetone, dimethoxyethane, dioxane, tetrahydrofuran,dimethylformamide, dimethylacetamide, dimethyl sulphoxide, ethanol,toluene or, if appropriate, mixtures of the diluents mentioned withwater.

Suitable diluents for carrying out the process (G) according to theinvention are in each case all customary inert organic solvents.Preference is given to using optionally halogenated aliphatic, alicyclicor aromatic hydrocarbons, such as petroleum ether, hexane, heptane,cyclohexane, methylcyclohexane, benzene, toluene, xylene or decaline;chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbontetrachloride, dichloroethane or trichloroethane; ethers, such asdiethyl ether, disopropyl ether, methyl tert-butyl ether, methyltert-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane,1,2-diethoxyethane or anisole. Particular preference is given to usingdioxane, tetrahydrofuran or toluene.

Suitable acid binders for carrying out the processes (D), (E), (F) and(G) according to the invention are in each case all inorganic andorganic bases which are customary for such reactions. Preference isgiven to using alkaline earth metal or alkali metal hydroxides, such assodium hydroxide, calcium hydroxide, potassium hydroxide, or elseammonium hydroxide, alkali metal carbonates, such as sodium carbonate,potassium carbonate, potassium bicarbonate, sodium bicarbonate, alkalimetal or alkaline earth metal acetates, such as sodium acetate,potassium acetate, calcium acetate, alkali metal fluorides, and alsotertiary amines, such as trimethylamine, triethylamine, tributylamine,N,N-dimethylaniline, pyridine, N-methylpiperidine,N,N-dimethylaminopyridine, diazabicyclooctane (DABCO),diazabicyclononene (DBN) or diazabicycloundecene (DBU). However, it isalso possible to operate without additional acid binder, or to employ anexcess of the amine component, so that it simultaneously acts as acidbinder. Barium hydroxide, sodium hydroxide, potassium hydroxide,tripotassium phosphate, caesium carbonate, potassium carbonate, sodiumcarbonate, potassium acetate, triethylamine, potassium tert-butoxide,caesium fluoride or potassium fluoride are used with particularpreference., When carrying out the processes (D), (E) and (F), thereaction temperatures can in each case be varied within a relativelywide range. In general, the reactions are carried out at temperaturesbetween 0° C. and 140° C., preferably between 20° C. and 120° C.,particularly preferably between 60° C. and 100° C.

When carrying out the process (G) according to the invention, thereaction temperatures can in each case be varied within a relativelywide range. In general, the reaction is carried out at temperaturesbetween 0° C. and 140° C., preferably between 20° C. and 120° C.

Chiral Compounds of the Formula (I-d)

To prepare chiral compounds of the formula (I-d), it is possible, forexample, to subject Δ¹-pyrrolines of the formula (I-e)

in which

-   R¹, R² and R³ have the meanings given above,-   Het⁶ represents heteroaryl which is monosubstituted by R⁵⁻⁴ and-   R⁵⁻⁴ represents chlorine, bromine or iodine    to an optical resolution. However, it is also possible to use other    compounds of the formula (I) according to the invention. To this    end, for example, methods of preparative chromatography, preferably    the high performance liquid chromatography (HPLC) method, are    employed. Here, a chiral stationary silica gel phase is used. A    tris-(3,5-dimethylphenylcarbamate)-cellulose-modified silica gel has    been found to be particularly suitable for separating the compounds    of the formula (I-e) into the two enantiomers. This separating    material is commercially available. However, it is also possible to    use other stationary phases. Suitable mobile phases are all    customary inert organic solvents, and mixtures of these. Preference    is given to using optionally halogenated aliphatic, alicyclic or    aromatic hydrocarbons, such as petroleum ether, hexane, heptane,    cyclohexane; dichloromethane, chloroform; alcohols, such as    methanol, ethanol, propanol; nitriles, such as acetonitrile; esters,    such as methyl acetate or ethyl acetate. Particular preference is    given to using aliphatic hydrocarbons, such as hexane or heptane,    and alcohols, such as methanol or propanol, very particularly    preferably n-heptane and isopropanol or mixtures of these.

In general, the separation is carried out at temperatures between 10° C.and 60° C., preferably between 10° C. and 40° C., particularlypreferably at room temperature.

Δ¹-Pyrrolines of the formula (I-e) form part of the subject-matter ofthis invention and can be prepared by one of the processes (A), (B) or(C). The (R)-configured enantiomers obtained in this manner are thenused as starting materials for the processes (D), (F) or (G).

All of the processes according to the invention are generally carriedout under atmospheric pressure. However, in each case it is alsopossible to operate under elevated or reduced pressure.

The active compounds, according to the invention, having good planttolerance and favourable warm-blood toxicity, are suitable forcontrolling animal pests, in particular insects, arachnids andnematodes, which are encountered in agriculture, in forestry, in theprotection of stored products and of materials, and in the hygienesector. They may be preferably used as crop protection agents. They areactive against normally sensitive and resistant species and against allor some stages of development. The abovementioned pests include:

From the order of the Isopoda, for example, Oniscus asellus,Armadillidium vulgare and Porcellio scaber.

From the order of the Diplopoda, for example, Blaniulus guttulatus.

From the order of the Chilopoda, for example, Geophilus carpophagus andScutigera spp.

From the order of the Symphyla, for example, Scutigerella immaculata.

From the order of the Thysanura, for example, Lepisma saccharina.

From the order of the Collembola, for example, Onychiurus armatus.

From the order of the Orthoptera, for example, Acheta domesticus,Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus spp. andSchistocerca gregaria.

From the order of the Blattaria, for example, Blatta orientalis,Periplaneta americana, Leucophaea maderae and Blattella germanica.

From the order of the Dermaptera., for example, Forficula auricularia.

From the order of the Isoptera, for example, Reticulitermes spp.

From the order of the Phthiraptera, for example, Pediculus humanuscorporis, Haematopinus spp., Linognathus spp., Trichodectes spp. andDamalinia spp.

From the order of the Thysanoptera, for example, Hercinothripsfemoralis, Thrips tabaci, Thrips palmi and Frankliniella accidentalis.

From the order of the Heteroptera, for example, Eurygaster spp.,Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodniusprolixus and Triatoma spp.

From the order of the Homoptera, for example, Aleurodes brassicae,Bemisia tabaci, Trialeurodes vaporaniorum, Aphis gossypii, Brevicorynebrassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosomalanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pemphigus spp.,Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi,Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecaniumcomi, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens,Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. and Psyllaspp.

From the order of the Lepidoptera, for example, Pectinophoragossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletisblancardella, Hyponomeuta padella, Plutella xylostella, Malacosomaneustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrixthurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltiaspp., Earias insulana, Heliothis spp., Mamestra brassicae, Panolisflammea, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pierisspp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleriamellonella, Tineola bisselliella, Tinea pellionella, Hofmannophilapseudospretella, Cacoecia podana, Capua reticulana, Choristoneurafumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana,Cnaphalocerus spp. and Oulema oryzae.

From the order of the Coleoptera, for example, Anobium punctatum,Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus,Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedoncochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachnavarivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp.,Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus,Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogodermaspp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus,Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp.,Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha,Amphimallon solstitialis, Costelytra zealandica and Lissorhoptrusoryzophilus.

From the order of the Hymenoptera, for example, Diprion spp., Hoplocampaspp., Lasius spp., Monomorium pharaonis and Vespa spp.

From the order of the Diptera, for example, Aedes spp., Anopheles spp.,Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphoraerythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp.,Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp.,Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinellafrit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae,Tipula paludosa, Hylemyia spp. and Liriomyza spp.

From the order of the Siphonaptera, for example, Xenopsylla cheopis andCeratophyllus spp.

From the class of the Arachnida, for example, Scorpio maurus,Latrodectus mactans, Acarus siro, Argas spp., Omithodoros spp.,Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora,Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp.,Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemusspp., Bryobia praetiosa, Panonychus spp., Tetranychus spp.,Hemitarsonemus spp. and Brevipalpus spp.

The plant-parasitic nematodes include, for example, Pratylenchus spp.,Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans,Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp.,Longidorus spp., Xiphinema spp., Trichodorus spp. and Bursaphelenchusspp.

The compounds of the formula (I) according to the invention areparticularly effective against caterpillars, beetle larvae, spidermites, aphids and leaf-mining flies.

At certain concentrations or application rates, the compounds accordingto the invention may, if appropriate, also be used as herbicides andmicrobicides, for example as fungicides, antimycotics and bactericides.If appropriate, they may also be used as intermediates or precursors forthe synthesis of further active compounds.

All plants and plant parts can be treated in accordance with theinvention. Plants are to be understood as meaning in the present contextall plants and plant populations such as desired and undesired wildplants or crop plants (inclusive of naturally occurring crop plants).Crop plants can be plants which can be obtained by conventional plantbreeding and optimization methods or by biotechnological and recombinantmethods or by combinations of these methods, inclusive of the transgenicplants and inclusive of the plant cultivars protectable or notprotectable by plant breeders' rights. Plant parts are to be understoodto mean all above-ground and underground parts and organs of plants,such as shoot, leaf, flower and root, examples which may be mentionedbeing leaves, needles, stalks, stems, flowers, fruit bodies, fruits,seeds, roots, tubers and rhizomes. The plant parts also includeharvested material, and vegetative and generative propagation material,for example cuttings, tubers, rhizomes, offsets and seeds.

Treatment according to the invention of the plants and plant parts withthe active compounds is carried out directly or by allowing thecompounds to act on their surroundings, environment or storage space bythe customary treatment methods, for example by immersion, spraying,evaporation, fogging, scattering, painting on and, in the case ofpropagation material, in particular in the case of seeds, also byapplying one or more coats.

The active compounds can be converted into the customary formulations,such as solutions, emulsions, wettable powders, suspensions, powders,dusts, pastes, soluble powders, granules, suspension-emulsionconcentrates, natural and synthetic materials impregnated with activecompound, and microencapsulations in polymeric substances.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is liquid solvents and/orsolid carriers, optionally with the use of surfactants, that isemulsifiers and/or dispersants, and/or foam-formers.

If the extender used is water, it is also possible to employ for exampleorganic solvents as auxiliary solvents. Essentially, suitable liquidsolvents are: aromatics such as xylene, toluene or alkylnaphthalenes,chlorinated aromatics or chlorinated aliphatic hydrocarbons such aschlorobenzenes, chloroethylenes or methylene chloride, aliphatichydrocarbons such as cyclohexane or paraffins, for example petroleumfractions, mineral and vegetable oils, alcohols such as butanol orglycol and also their ethers and esters, ketones such as acetone, methylethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polarsolvents such as dimethylformamide and dimethyl sulphoxide, and alsowater.

Suitable solid carriers are:

for example ammonium salts and ground natural minerals such as kaolins,clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceousearth, and ground synthetic minerals, such as finely divided silica,alumina and silicates; suitable solid carriers for granules are: forexample crushed and fractionated natural rocks such as calcite, marble,pumice, sepiolite and dolomite, and also synthetic granules of inorganicand organic meals, and granules of organic material such as sawdust,coconut shells, maize cobs and tobacco stalks; suitable emulsifiersand/or foam-formers are: for example nonionic and anionic emulsifiers,such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcoholethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkylsulphates, arylsulphonates and, also protein hydrolysates; suitabledispersants are: for example lignosulphite waste liquors andmethylcellulose.

Tackifiers such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, as well as naturalphospholipids such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations. Other additives can bemineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyes, such asalizarin dyes, azo dyes and metal phthalocyanine dyes, and tracenutrients such as salts of iron, manganese, boron, copper, cobalt,molybdenum and zinc.

The formulations generally comprise between 0.1 and 95% by weight ofactive compound, preferably between 0.5 and 90%.

The active compound according to the invention can be present in itscommercially available formulations and in the use forms, prepared fromthese formulations, as a mixture with other active compounds, such asinsecticides, attractants, sterilizing agenis, bactericides, acaricides,nematicides, fungicides, growth-regulating substances or herbicides. Theinsecticides include, for example, phosphoric acid esters, carbamates,carboxylates, chlorinated hydrocarbons, phenylureas and substancesproduced by microorganisms, inter alia.

Particularly favourable examples of co-components in mixtures are thefollowing compounds:

Fungicides:

-   aldimorph, ampropylfos, ampropylfos-potassium, andoprim, anilazine,    azaconazole, azoxystrobin,-   benalaxyl, benodanil, benomyl, benzamacril, benzamacril-isobutyl,    bialaphos, binapacryl, biphenyl, bitertanol, blasticidin-S,    bromuconazole, bupirimate, buthiobate,-   calcium polysulphide, capsimycin, captafol, captan, carbendazim,    carboxin, carvon, quinomethionate, chlobenthiazone, chlorfenazole,    chloroneb, chloropicrin, chlorothalonil, chlozolinate, clozylacon,    cufraneb, cymoxanil, cyproconazole, cyprodinil, cyprofuram,-   debacarb, dichlorophen, diclobutrazole, diclofluanid, diclomezine,    dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph,    diniconazole, diniconazole-M, dinocap, diphenylamine, dipyrithione,    ditalimfos, dithianon, dodemorph, dodine, drazoxolon,-   edifenphos, epoxiconazole, etaconazole, ethirimol, etridiazole,-   famoxadon, fenapanil, fenarimol, fenbuconazole, fenfuram,    fenitropan, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate,    fentin hydroxide, ferbam, ferimzone, fluazinam, flumetover,    fluoromide, fluquinconazole, flurprimidol, flusilazole,    flusulfamide, flutolanil, flutriafol, folpet, fosetyl-aluminium,    fosetyl-sodium, fthalide, fuberidazole, furalaxyl, furametpyr,    furcarbonil, furconazole, furconazole-cis, furmecyclox,-   guazatine,-   hexachlorobenzene, hexaconazole, hymexazole,-   imazalil, imibenconazole, iminoctadine, iminoctadine albesilate,    iminoctadine triacetate, iodocarb, ipconazole, iprobenfos (IBP),    iprodione, irumamycin, isoprothiolane, isovaledione,-   kasugamycin, kresoxim-methyl, copper preparations, such as: copper    hydroxide, copper naphthenate, copper oxychloride, copper sulphate,    copper oxide, oxine-copper and Bordeaux mixture,-   mancopper, mancozeb, maneb, meferimzone, mepanipyrim, mepronil,    metalaxyl,-   metconazole, methasulfocarb, methfuroxam, metiram, metomeclam,    metsulfovax, mildiomycin, myclobutanil, myclozplin,-   nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol,-   ofurace, oxadixyl, oxamocarb, oxolinic acid, oxycarboxim;    oxyfenthiin,-   paclobutrazole, pefurazoate, penconazole, pencycuron, phosdiphen,    pimaricin, piperalin, polyoxin, polyoxorim, probenazole, prochloraz,    procymidone, propamocarb, propanosine-sodium, propiconazole,    propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon,    pyroxyfur,-   quinconazole, quintozene (PCNB),-   sulphur and sulphur preparations,-   tebuconazole, tecloftalam, tecnazene, tetcyclacis, tetraconazole,    thiabendazole, thicyofen, thifluzamide, thiophanate-methyl, thiram,    tioxymid, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol,    triazbutil, triazoxide, trichlamide, tricyclazole, tridemorph,    triflumizole, triforine, triticonazole,-   uniconazole,-   validamycin A, vinclozolin, viniconazole,-   zarilamide, zineb, ziram and also-   Dagger G,-   OK-8705, OK-8801,-   α-(1,1-dimethylethyl)-β-(2-phenoxyethyl)-1H-1,2,4-triazole-1-ethanol,-   α-(2,4-dichlorophenyl)-β-fluoro-β-propyl-1H-1,2,4-triazole-1-ethanol,-   α-(2,4-dichlorophenyl)-β-methoxy-α-methyl-1H-1,2,4-triazole-1-ethanol,-   α-(5-methyl-1,3-dioxan-5-yl)-β-[[4-(trifluoromethyl)-phenyl]-methylene]-1H-1,2,4-triazole-1-ethanol,-   (5RS,6RS)-6-hydroxy-2,2,7,7-tetramethyl-5-(1H-1,2,4-triazol-1-yl)-3-octanone,    (E)-α-(methoxyimino)-N-methyl-2-phenoxy-phenylacetamide,-   isopropyl    {2-methyl-1-[[[1-(4-methylphenyl)-ethyl]-amino]-carbonyl]-propyl}-carbamate,-   1-(2,4-dichlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-ethanone-O-(phenylmethyl)-oxime,-   1-(2-methyl-1-naphthalenyl)-1H-pyrrole-2,5-dione,-   1-(3,5-dichlorophenyl)-3-(2-propenyl)-2,5-pyrrolidinedione,-   1-[(diiodomethyl)-sulphonyl]4-methyl-benzene,-   1-[[2-(2,4-dichlorophenyl)-1,3-dioxolan-2-yl]-methyl]-1H-imidazole,-   1-[[2-(4-chlorophenyl)-3-phenyloxiranyl]-methyl]-1H-1,2,4-triazole,-   1-[1-[2-[(2,4-dichlorophenyl)-methoxy]-phenyl]-ethenyl]-1H-imidazole,-   1-methyl-5-nonyl-2-(phenylmethyl)-3-pyrrolidinol,-   2′,6′-dibromo-2-methyl-4′-trifluoromethoxy-4′-trifluoro-methyl-1,3-thiazole-5-carboxanilide,-   2,2-dichloro-N-[1-(4-chlorophenyl)-ethyl]-1-ethyl-3-methyl-cyclopropanecarboxamide,-   2,6-dichloro-5-(methylthio)-4-pyrimidinyl-thiocyanate,-   2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide,-   2,6-dichloro-N-[[4-(trifluoromethyl)-phenyl]-methyl]-benzamide,-   2-(2,3,3-triiodo-2-propenyl)-2H-tetrazole,-   2-[(1-methylethyl)-sulphonyl]-5-(trichloromethyl)-1,3,4-thiadiazole,-   2-[[6-deoxy-4-O-(4-O-methyl-β-D-glycopyranosyl)-α-D-glucopyranosyl]-amino]-4-methoxy-1H-pyrrolo[2,3-d]pyrimidine-5-carbonitrile,-   2-aminobutane,-   2-bromo-2-(bromomethyl)-pentanedinitrile,-   2-chloro-N-(2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl)-3-pyridinecarboxamide,-   2-chloro-N-(2,6-dimethylphenyl)-N-(isothiocyanatomethyl)-acetamide,-   2-phenylphenol (OPP),-   3,4-dichloro-1-[4-(difluoromethoxy)-phenyl]-1H-pyrrole-2,5-dione,-   3,5-dichloro-N-[cyano-[(1-methyl-2-propynyl)-oxy]-methyl]-benzamide,-   3-(1,1-dimethylpropyl)-1-oxo-1H-indene-2-carbonitrile,-   3-[2-(4-chlorophenyl)-5-ethoxy-3-isoxazolidinyl]-pyridine,-   4-chloro-2-cyano-N,N-dimethyl-5-(4-methylphenyl)-1H-imidazole-1-sulphonamide,-   4-methyl-tetrazolo[1,5-a]quinazolin-5(4H)-one,-   8-(1,1-dimethylethyl)-N-ethyl-N-propyl-1,4-dioxaspiro[4.5]decane-2-methanamine,-   8-hydroxyquinoline sulphate,-   9H-xanthene-2-[(phenylamino)-carbonyl]-9-carboxylic hydrazide,-   bis-(1-methylethyl)-3-methyl-4-[(3-methylbenzoyl)-oxy]-2,5-thiophenedicarboxylate,-   cis-1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-cycloheptanol,-   cis-4-[3-[4-(1,1-dimethylpropyl)-phenyl-2-methylpropyl]-2,6-dimethyl-morpholinehydrochloride,-   ethyl [(4-chlorophenyl)-azo]-cyanoacetate,-   potassium hydrogen carbonate,-   methanetetrathiol sodium salt,-   methyl    1-(2,3-dihydro-2,2-dimethyl-1H-inden-1-yl)-1H-imidazole-5-carboxylate,-   methyl N-(2,6-dimethylphenyl)-N-(5-isoxazolylcarbonyl)-DL-alaninate,-   methyl N-(chloroacetyl)-N-(2,6-dimethylphenyl)-DL-alaninate,-   N-(2,3-dichloro-4-hydroxyphenyl)-1-methyl-cyclohexanecarboxamide,-   N-(2,6-dimethylphenyl-2-methoxy-N-(tetrahydro-2-oxo-3-furanyl)-acetamide,-   N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-thienyl)-acetamide,-   N-(2-chloro-4-nitrophenyl)-4-methyl-3-nitro-benzenesulphonamide,-   N-(4-cyclohexylphenyl)-1,4,5,6-tetrahydro-2-pyrimidinamine,-   N-(4-hexylphenyl)-1,4,5,6-tetrahydro-2-pyrimidinamine,-   N-(5-chloro-2-methylphenyl)-2-methoxy-N-(2-oxo-3-oxazolidinyl)-acetamide,-   N-(6-methoxy)-3-pyridinyl)-cyclopropanecarboxamide,-   N-[2,2,2-trichloro-1-[(chloroacetyl)-amino]-ethyl]-benzamide,-   N-[3-chloro-4,5-bis-(2-propinyloxy)-phenyl]-N′-methoxy-methanimidamide,-   N-formyl-N-hydroxy-DL-alanine sodium salt,-   O,O-diethyl    [2-(dipropylamino)-2-oxoethyl]-ethylphosphoramidothioate,-   O-methyl S-phenyl phenylpropylphosphoramidothioate,-   S-methyl 1,2,3-benzothiadiazole-7-carbothioate,-   spiro[2H]-1-benzopyrane-2,1′(3′H)-isobenzofuran-3′-one.    Bactericides:-   bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate,    kasugamycin, octhilinone, furancarboxylic acid, oxytetracyclin,    probenazole, streptomycin, tecloftalam, copper sulphate and other    copper preparations.    Insecticides/Acaricides/Nematicides:-   abamectin, acephate, acetamiprid, acrinathrin, alanycarb, aldicarb,    aldoxycarb, alpha-cypermethrin, alphamethrin, amitraz, avermectin,    AZ 60541, azadirachtin, azamethiphos, azinphos A, azinphos M,    azocyclotin,-   Bacillus popilliae, Bacillus sphaericus, Bacillus subtilis, Bacillus    thuringiensis, Baculoviruses, Beauveria bassiana, Beauvena tenella,    bendiocarb, benfuracarb, bensultap, benzoximate, betacyfluthrin,    bifenazate, bifenthrin, bioethanomethrin, biopermethrin, BPMC,    bromophos A, bufencarb, buprofezin, butathiofos, butocarboxim,    butylpyridaben,-   cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan,    cartap, chloethocarb, chlorethoxyfos, chlorfenapyr, chlorfenvinphos,    chlorfluazuron, chlormephos, chlorpyrifos, chlorpyrifos M,    chlovaporthrin, cis-resmethrin, cis-permethrin, clocythrin,    cloethocarb, clofentezine, clothianidine, cyanophos, cycloprene,    cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin,    cyromazine, deltamethrin, demeton M, demeton S, demeton-S-methyl,    diafenthiuron, diazinon, dichlorvos, diflubenzuron, dimethoate,    dimethylvinphos, diofenolan, disulfoton, docusat-sodium, dofenapyn,-   eflusilanate, emamectin, empenthrin, endosulfan, Entomopfthora spp.,    eprinomectin, esfenvalerate, ethiofencarb, ethion, ethoprophos,    etofenprox, etoxazole, etrimfos, fenamiphos, fenazaquin, fenbutatin    oxide, fenitrothion, fenothiocarb, fenoxacrim, fenoxycarb,    fenpropathrin, fenpyrad, fenpyrithrin, fenpyroximate, fenvalerate,    fipronil, fluazuron, flubrocythrinate, flucycloxuron, flucythrinate,    flufenoxuron, flutenzine, fluvalinate, fonophos, fosmethilan,    fosthiazate, fubfenprox, furathiocarb, granulosis viruses,-   halofenozide, HCH, heptenophos, hexaflumuron, hexythiazox,    hydroprene,-   imidacloprid, isazofos, isofenphos, isoxathion, ivermectin,-   nuclear polyhedrosis viruses,-   lambda-cyhalothrin, lufenuron,-   malathion, mecarbam, metaldehyde, methamidophos, metharhizium    anisopliae, metharhizium flavoviride, methidathion, methiocarb,    methomyl, methoxyfenozide, metolcarb, metoxadiazone, mevinphos,    milbemectin, monocrotophos,-   naled, nitenpyram, nithiazine, novaluron,-   omethoate, oxamyl, oxydemethon M,-   Paecilomyces fumosoroseus, parathion A, parathion M, permethrin,    phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim,    pirimicarb; pirimiphos A, pirimiphos M, profenofos, promecarb,    propoxur, prothiofos, prothoate, pymetrozine, pyraclofos,    pyresmethrin, pyrethrum, pyridaben, pyridathion, pyrimidifen,    pyriproxyfen,-   quinalphos,-   ribavirin,-   salithion, sebufos, selamectin, silafluofen, spinosad, sulfotep,    sulprofos,-   tau-fluvalinate, tebufenozide, tebufenpyrad, tebupirimiphos,    teflubenzuron, tefluthrin, temephos, temivinphos, terbufos,    tetrachlorvinphos, thetacypermethrin, thiamethoxam, thiapronil,    thiatriphos, thiocyclam hydrogen oxalate, thiodicarb, thiofanox,    thuringiensin, tralocythrin, tralomethrin, triarathene, triazamate,    triazophos, triazurone, trichlophenidine, tnichlorfon, triflumuron,    trimethacarb,-   vamidothion, vaniliprole, Verticillium lecanii,-   YI 5302,-   zeta-cypermethrin, zolaprofos,-   (1R-cis)-[5-(phenylmethyl)-3-furanyl]-methyl    3-[(dihydro-2-oxo-3(2H)-furanylidene)-methyl]-2,2-dimethylcyclopropanecarboxylate,-   (3-phenoxyphenyl)-methyl 2,2,3,3-tetramethylcyclopropanecarboxylate,-   1-[(2-chloro-5-thiazolyl)methyl]tetrahydro-3,5-dimethyl-N-nitro-1,3,5-triazine-2(1H)-imine,-   2-(2-chloro-6-fluorophenyl)-4-[4-(1,1-dimethylethyl)phenyl]-4,5-dihydro-oxazole,-   2-(acetyloxy)-3-dodecyl-1,4-naphthalenedione,-   2-chloro-N-[[[4-(1-phenylethoxy)-phenyl]-amino]-carbonyl]-benzamide,-   2-chloro-N-[[[4-(2,2-dichloro-1,1-difluoroethoxy)-phenyl]-amino]-carbonyl]-benzamide,-   3-methylphenyl propylcarbamate,-   4-[4-(4-ethoxyphenyl)-4-methylpentyl]-1-fluoro-2-phenoxy-benzene,-   4-chloro-2-(1,1-dimethylethyl)-5-[[2-(2,6-dimethyl-4-phenoxyphenoxy)ethyl]thio]-3(2H)-pyridazinone,-   4-chloro-2-(2-chloro-2-methylpropyl)-5-[(6-iodo-3-pyridinyl)methoxy]-3(H)-pyridazinone,-   4-chloro-5-[(6-chloro-3-pyridinyl)methoxy]-2-(3,4-dichlordphenyl)-3(2H)-pyridazinone,-   Bacillus thuringiensis strain EG-2348,-   [2-benzoyl-1-(1,1-dimethylethyl)-hydrazinobenzoic acid,-   2,2-dimethyl-3-(2,4-dichlorophenyl)-2-oxo-1—oxaspiro[4.5]dec-3-en-4-yl    butanoate,-   [3-[(6-chloro-3-pyridinyl)methyl]-2-thiazolidinylidene]-cyanamide,-   dihydro-2-(nitromethylene)-2H-1,3-thiazine-3(4H)-carboxaldehyde,-   ethyl    [2-[[1,6-dihydro-6-oxo-1-(phenylmethyl)-4-pyridazinyl]oxy]ethyl]-carbamate,-   N-(3,4,4-trifluoro-1-oxo-3-butenyl)-glycine,-   N-(4-chlorophenyl)-3-[4-(difluoromethoxy)phenyl]-4,5-dihydro-4-phenyl-1H-pyrazole-1-carboxamide,-   N-[(2-chloro-5-thiazolyl)methyl]-N′-methyl-N″-nitro-guanidine,-   N-methyl-N′-(1-methyl-2-propenyl)-1,2-hydrazinedicarbothioamide,-   N-methyl-N′-2-propenyl-1,2-hydrazinedicarbothioamide,-   O,O-diethyl    [2-(dipropylamino)-2-oxoethyl]-ethylphosphoramidothioate.

A mixture with other known active compounds, such as herbicides, or withfertilizers and growth regulators is also possible.

The active compounds according to the invention can furthermore bepresent when used as insecticides in their commercially availableformulations and in the use forms, prepared from these formulations, asa mixture with synergistic agents.

Synergistic agents are compounds which increase the action of the activecompounds, without it being necessary for the synergistic agent added tobe active itself.

The active compound content of the use forms prepared from thecommercially available formulations can vary within wide limits. Theactive compound concentration of the use forms can be from 0.0000001 to95% by weight of active compound, preferably between 0.0001 and 1% byweight.

The compounds are employed in a customary manner appropriate for the useforms.

When used against hygiene pests and pests of stored products, the activecompound is distinguished by an excellent residual action on wood andclay as well as a good stability to alkali on limed substrates.

As already mentioned above, it is possible to treat all plants and theirparts according to the invention. In a preferred embodiment, wild plantspecies and plant cultivars, or those obtained by conventionalbiological breeding, such as crossing or protoplast fusion, and partsthereof, are treated. In a further preferred embodiment, transgenicplants and plant cultivars obtained by genetic engineering, ifappropriate in combination with conventional methods (GeneticallyModified Organisms), and parts thereof are treated. The term “parts” or“parts of plants” or “plant parts” has been explained above.

Particularly preferably, plants of the plant cultivars which are in eachcase commercially available or in use are treated according to theinvention. Plant cultivars are to be understood as meaning plants havingcertain properties (“traits”) which have been obtained by conventionalbreeding, by mutagenesis or by recombinant DNA techniques. This can bevarieties, bio- and genotypes.

Depending on the plant species or plant cultivars, their location andgrowth conditions (soils, climate, vegetation period, diet), thetreatment according to the invention may also result in superadditive(“synergistic”) effects. Thus, for example, reduced application ratesand/or a widening of the activity spectrum and/or an increase in theactivity of the substances and compositions to be used according to theinvention, better plant growth, increased tolerance to high or lowtemperatures, increased tolerance to drought or to water or soil saltcontent, increased flowering performance, easier harvesting, acceleratedmaturation, higher harvest yields, better quality and/or a highernutritional value of the harvested products, better storage stabilityand/or processability of the harvested products are possible whichexceed the effects which were actually to be expected.

The transgenic plants or plant cultivars (i.e. those obtained by geneticengineering) which are preferred according to the invention include allplants which, in the genetic modification, received genetic materialwhich imparted particularly advantageous useful traits to these plants.Examples of such traits are better plant growth, increased tolerance tohigh or low temperatures, increased tolerance to drought or to water orsoil salt content, increased flowering performance, easier harvesting,accelerated maturation, higher harvest yields, better quality and/or ahigher nutritional value of the harvested products, better storagestability and/or processability of the harvested products. Further andparticularly emphasized examples of such traits are a better defence ofthe plants against animal and microbial pests, such as against insects,mites, phytopathogenic fungi, bacteria and/or viruses, and alsoincreased tolerance of the plants to certain herbicidally activecompounds. Examples of transgenic plants which may be mentioned are theimportant crop plants, such as cereals (wheat, rice), maize, soya beans,potatoes, cotton, oilseed rape and also fruit plants (with the fruitsapples, pears, citrus fruits and grapevines), and particular emphasis isgiven to maize, soya beans, potatoes, cotton and oilseed rape. Traitsthat are emphasized are in particular increased defence of the plantsagainst insects by toxins formed in the plants, in particular thoseformed by the genetic material from Bacillus thuringiensis (for exampleby the genes CryIA(a), CryIA(b), CryIA(c), CryIIA, CryIIIA, CryIIIB2,Cry9c, Cry2Ab, Cry3Bb and CryIF and also combinations thereof)(hereinbelow referred to as “Bt plants”). Traits that are alsoparticularly emphasized are the increased defence of the plants tofungi, bacteria and viruses by systemic acquired resistance (SAR),systemin, phytoalexius, elicitous and resistance genes andcorrespondingly expressed proteins and toxins. Traits that arefurthermore particularly emphasized are the increased tolerance of theplants to certain herbicidally active compounds, for exampleimidazolinones, sulphonylureas, glyphosate or phosphinotricin (forexample the “PAT” gene). The genes which impart the desired traits inquestion can also be present in combination with one another in thetransgenic plants. Examples of “Bt plants” which may be mentioned aremaize varieties, cotton varieties, soya bean varieties and potatovarieties which are sold under the trade names YIELD GARD® (for examplemaize, cotton, soya beans), KnockOut® (for example maize), StarLink®(for example maize), Bollgard® (cotton), Nucotn® (cotton) and NewLeaf®(potato). Examples of herbicide-tolerant plants which may be mentionedare maize varieties, cotton varieties and soya bean varieties which aresold under the trade names Roundup Ready® (tolerance to glyphosate, forexample maize, cotton, soya bean), Liberty Link® (tolerance tophosphinotricin, for example oilseed rape), IMI® (tolerance toimidazolinones) and STS® (tolerance to sulphonylureas, for examplemaize). Herbicide-resistant plants (plants bred in a conventional mannerfor herbicide tolerance) which may be mentioned include the varietiessold under the name Clearfield® (for example maize). Of course, thesestatements also apply to plant cultivars having these orstill-to-be-developed genetic traits, which plants will be developedand/or marketed in the future.

The plants listed can be treated according to the invention in aparticularly advantageous manner with the compounds of the generalformula (I) or the active compound mixtures according to the invention.The preferred ranges stated above for the active compounds or mixturesalso apply to the treatment of these plants.

Particular emphasis is given to the treatment of plants with thecompounds or the mixtures specifically mentioned in the present text.

The active compounds according to the invention act not only againstplant, hygiene and stored product pests, but also in the veterinarymedicine sector against animal parasites (ectoparasites), such as hardticks, soft ticks, mange mites, leaf mites, flies (biting and licking),parasitic fly larvae, lice, hair lice, feather lice and fleas. Theseparasites include:

From the order of the Anoplurida, for example, Haematopinus spp.,Linognathus spp., Pediculus spp., Phtirus spp. and Solenopotes spp.

From the order of the Mallophagida and the suborders Amblycerina andIschnocerina, for example, Trimenopon spp., Menopon spp., Trinoton spp.,Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp.,Trichodectes spp. and Felicola spp.

From the order Diptera and the suborders Nematocerina and Brachycerina,for example, Aedes spp., Anopheles spp., Culex spp., Simulium spp.,Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp.,Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopotaspp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp.,Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossinaspp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp.,Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp.,Hippobosca spp., Lipoptena spp. and Melophagus spp.

From the order of the Siphhonapterida, for example, Pulex spp.,Ctenocephalides spp., Xenopsylla spp. and Ceratophyllus spp.

From the order of the Heteropterida, for example, Cimex spp., Triatomaspp., Rhodnius spp. and Panstrongylus spp.

From the order of the Blattarida, for example, Blatta orientalis,Periplaneta americana, Blattela germanica and Supella spp.

From the subclass of the Acaria (Acarida) and the orders of the Meta-and Mesostigmata, for example, Argas spp., Ornithodorus spp., Otobiusspp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp.,Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp.,Raillietia spp., Pneumonyssus spp., Stemostoma spp. and Varroa spp.

From the order of the Actinedida (Prostigmata) and Acaridida(Astigmata), for example, Acarapis spp., Cheyletiella spp.,Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp.,Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp.,Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp.,Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp.,Knemidocoptes spp., Cytodites spp. and Laminosioptes spp.

These are highly effective, for example, against the development stagesof ticks, for example Amblyomma hebraeum, against parasitic flies, forexample against Lucilia cuprina, and against fleas, for example againstCtenocephalides felis.

The active compounds of the formula (I) according to the invention arealso suitable for controlling arthropods which infest agriculturalproductive livestock, such as, for example, cattle, sheep, goats,horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys,ducks, geese and bees, other pets, such as, for example, dogs, cats,caged birds and aquarium fish, and also so-called test animals, such as,for example, hamsters, guinea pigs, rats and mice. By controlling thesearthropods, cases of death and reduction in productivity (for meat,milk, wool, hides, eggs, honey etc.) should be diminished, so that moreeconomic and easier animal husbandry is possible by use of the activecompounds according to the invention.

The active compounds according to the invention are used in theveterinary sector in a known manner by enteral administration in theform of, for example, tablets, capsules, potions, drenches, granules,pastes, boluses, the feed-through process and suppositories, byparenteral administration, such as, for example, by injections(intramuscular, subcutaneous, intravenous, intraperitoneal and thelike), implants, by nasal administration, by dermal use in the form, forexample, of dipping or bathing, spraying, pouring on and spotting on,washing and powdering, and also with the aid of moulded articlescontaining the active compound, such as collars, ear marks, tail marks,limb bands, halters, marking devices and the like.

When used for cattle, poultry, pets and the like, the active compoundsof the formula (I) according to the invention can be used asformulations (for example, powders, emulsions, free-flowingcompositions), which comprise the active compounds according to theinvention in an amount of 1 to 80% by weight, directly or after 100 to10 000-fold dilution, or they can be used as a chemical bath.

It has furthermore been found that the compounds according to theinvention also have a strong insecticidal action against insects whichdestroy industrial materials.

The following insects may be mentioned as examples and as beingpreferred—but without any limitation:

Beetles, such as

-   Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum,    Xestobium rufdvillosum, Ptilinus pecticornis, Dendrobium pertinex,    Emobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus,    Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon    aequale, Minthes rugicollis, Xyleborus spec., Tryptodendron spec.,    Apate monachus, Bostrychus capucins, Heterobostrychus brunneus,    Sinoxylon spec. and Dinoderus minutus.    Hymenopterons, such as-   Sirex juvencus, Urocerus gigas, Urocerus gigas taignus and Urocerus    augur.    Termites, such as-   Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola,    Reticuliterrnes flavipes, Reticulitermes santonensis, Reticulitermes    lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis and    Coptotermes formosanus.-   Bristletails, such as Lepisma saccharina.

Industrial materials in the present context are to be understood asmeaning non-living materials, such as, preferably, plastics, adhesives,sizes, papers and cards, leather, wood and processed wood products andcoating compositions.

Wood and processed wood products are materials to be protected,especially preferably, from insect infestation.

Wood and processed wood products which can be protected by the agentaccording to the invention or mixtures comprising this are to beunderstood as meaning, for example:

-   building timber, wooden beams, railway sleepers, bridge components,    boat jetties, wooden vehicles, boxes, pallets, containers, telegraph    poles, wood panelling, wooden windows and doors, plywood, chipboard,    joinery or wooden products which are used quite generally in    house-building or in building joinery.

The active compounds according to the invention can be used as such, inthe form of concentrates or in generally customary formulations, such aspowders, granules, solutions, suspensions, emulsions or pastes.

The formulations mentioned can be prepared in a manner known per se, forexample by mixing the active compounds according to the invention withat least one solvent or diluent, emulsifier, dispersing agent and/orbinder or fixing agent, a water repellent, if appropriate siccatives andUV stabilizers and if appropriate dyes and pigments, and also otherprocessing auxiliaries.

The insecticidal compositions or concentrates used for the preservationof wood and wood-derived timber products comprise the active compoundaccording to the invention in a concentration of 0.0001 to 95% byweight, in particular 0.001 to 60% by weight.

The amount of the compositions or concentrates employed depends on thenature and occurrence of the insects and on the medium. The optimumamount employed can be determined for the use in each case by a seriesof tests. In general, however, it is sufficient to employ 0.0001 to 20%by weight, preferably 0.001 to 10% by weight, of the active compound,based on the material to be preserved.

Solvents and/or diluents which are used are an organic chemical solventor solvent mixture and/or an oily or oil-like organic chemical solventor solvent mixture of low volatility and/or a polar organic chemicalsolvent or solvent mixture and/or water, and if appropriate anemulsifier and/or wetting agent.

Organic chemical solvents which are preferably used are oily or oil-likesolvents having an evaporation number above 35 and a flashpoint above30° C., preferably above 45° C. Substances which are used as such oilyor oil-like water-insoluble solvents of low volatility are appropriatemineral oils or aromatic fractions thereof, or solvent mixturescontaining mineral oils, preferably white spirit, petroleum and/oralkylbenzene.

Mineral oils having a boiling range from 170 to 220° C., white spirithaving a boiling range from 170 to 220° C., spindle oil having a boilingrange from 250 to 350° C., petroleum and aromatics having a boilingrange from 160 to 280° C., turpentine oil and the like, areadvantageously employed.

In a preferred embodiment, liquid aliphatic hydrocarbons having aboiling range from 180 to 210° C. or high-boiling mixtures of aromaticand aliphatic hydrocarbons having a boiling range from 180 to 220° C.and/or spindle oil and/or monochloronaphthalene, preferablyα-monochloronaphthalene, are used.

The organic oily or oil-like solvents of low volatility which have anevaporation number above 35 and a flashpoint above 30° C., preferablyabove 45° C., can be replaced in part by organic chemical solvents ofhigh or medium volatility, providing that the solvent mixture likewisehas an evaporation number above 35 and a flashpoint above 30° C.,preferably above 45° C., and that the insecticide/fungicide mixture issoluble or emulsifiable in this solvent mixture.

According to a preferred embodiment, some of the organic chemicalsolvent or solvent mixture is replaced by an aliphatic polar organicchemical solvent or solvent mixture. Aliphatic organic chemical solventscontaining hydroxyl and/or ester and/or ether groups, such as, forexample, glycol ethers, esters or the like, are preferably used.

Organic chemical binders which are used in the context of the presentinvention are the synthetic resins and/or binding drying oils which areknown per se, are water-dilutable and/or are soluble or dispersible oremulsifiable in the organic chemical solvents employed, in particularbinders consisting of or comprising an acrylate resin, a vinyl resin,for example polyvinyl acetate, polyester resin, polycondensation orpolyaddition resin, polyurethane resin, alkyd resin or modified alkydresin, phenolic resin, hydrocarbon resin, such as indene-cumarone resin,silicone resin, drying vegetable oils and/or drying oils and/orphysically drying binders based on a natural and/or synthetic resin.

The synthetic resin used as the binder can be employed in the form of anemulsion, dispersion or solution. Bitumen or bituminous substances canalso be used as binders in an amount of up to 10% by weight. Dyestuffs,pigments, water-repelling agents, odour correctants and inhibitors oranticorrosive agents and the like which are known per se canadditionally be employed.

It is preferred according to the invention for the composition orconcentrate to comprise, as the organic chemical binder, at least onealkyd resin or modified alkyd resin and/or one drying vegetable oil.Alkyd resins having an oil content of more than 45% by weight,preferably 50 to 68% by weight, are preferably used according to theinvention.

All or some of the binder mentioned can be replaced by a fixing agent(mixture) or a plasticizer (mixture). These additives are intended toprevent evaporation of the active compounds and crystallization orprecipitation. They preferably replace. 0.01 to 30% of the binder (basedon 100% of the binder employed).

The plasticizers originate from the chemical classes of phthalic acidesters, such as dibutyl, dioctyl or benzyl butyl phthalate, phosphoricacid esters, such as tributyl phosphate, adipic acid esters, such asdi-(2-ethylhexyl) adipate, stearates, such as butyl stearate or amylstearate, oleates, such as butyl oleate, glycerol ethers or highermolecular weight glycol ethers, glycerol esters and p-toluenesulphonicacid esters.

Fixing agents are based chemically on polyvinyl alkyl ethers, such as,for example, polyvinyl methyl ether or ketones, such as benzophenone orethylenebenzophenone.

Possible solvents or diluents are, in particular, also water, ifappropriate as a mixture with one or more of the abovementioned organicchemical solvents or diluents, emulsifiers and dispersing agents.

Particularly effective preservation of wood is achieved by impregnationprocesses on a large industrial scale, for example vacuum, double vacuumor pressure processes.

The ready-to-use compositions can also comprise other insecticides, ifappropriate, and also one or more fungicides, if appropriate.

Possible additional mixing partners are, preferably, the insecticidesand fungicides mentioned in WO 94/29 268. The compounds mentioned inthis document are an explicit constituent of the present application.

Especially preferred mixing partners which may be mentioned areinsecticides, such as chlorpyriphos, phoxim, silafluofin, alphamethrin,cyfluthrin, cypernethrin, deltamethrin, permethrin, imidacloprid, NI-25,flufenoxuron, hexaflumuron, transfluthrin, thiacloprid, methoxyphenoxideand triflumuron, and also fungicides, such as epoxyconazole,hexaconazole, azaconazole, propiconazole, tebuconazole, cyproconazole,metconazole, imazalil, dichlorfluanid, tolylfluanid,3-iodo-2-propinyl-butyl carbamate, N-octyl-isothiazolin-3-one and4,5-dichloro-N-octylisothiazolin-3-one.

The compounds according to the invention can at the same time beemployed for protecting objects which come into contact with salt wateror brackish water, such as hulls, screens, nets, buildings, moorings andsignalling systems, against fouling.

Fouling by sessile Oligochaeta, such as Serpulidae, and by shells andspecies from the Ledamorpha group (goose barnacles), such as variousLepas and Scalpellum species, or by species from the Balanomorpha group(acorn barnacles), such as Balanus or Pollicipes species, increases thefrictional drag of ships and, as a consequence, leads to a markedincrease in operation costs owing to higher energy consumption andadditionally frequent residence in the dry dock.

Apart from fouling by algae, for example Ectocarpus sp. and Ceramiumsp., fouling by sessile Entomostraka groups, which come under thegeneric term Cirripedia (cirriped crustaceans), is of particularimportance.

Surprisingly, it has now been found that the compounds according to theinvention, alone or in combination with other active compounds, have anoutstanding antifouling action.

Using the compounds according to the invention, alone or in combinationwith other active compounds, allows the use of heavy metals such as, forexample, in bis-(trialkyltin) sulphides, tri-n-butyltin laurate,tri-n-butyltin chloride, copper(I) oxide, triethyltin chloride,tri-n-butyl-(2-phenyl-4-chlorophenoxy)tin, tributyltin oxide, molybdenumdisulphide, antimony oxide, polymeric butyl titanate,phenyl-(bispyridine)-bismuth chloride, tri-n-butyltin fluoride,manganese ethylenebisthio-carbamate, zinc dimethyldithiocarbamate, zincethylenebisthiocarbamate, zinc salts and copper salts of 2-pyridinethiol1-oxide, bisdimethyldithiocarbamoylzinc ethylene-bisthiocarbamate, zincoxide, copper(I) ethylene-bisdithiocarbamate, copper thiocyanate, coppernaphthenate and tributyltin halides to be dispensed with, or theconcentration of these compounds to be substantially reduced.

If appropriate, the ready-to-use antifouling paints can additionallycomprise other active compounds, preferably algicides, fungicides,herbicides, molluscicides, or other antifouling active compounds.

Preferably suitable components in combinations with the antifoulingcompositions according to the invention are:

Algicides such as

-   2-tert-butylamino-4-cyclopropylamino-6-methylthio-1,3,5-triazine,    dichlorophen, diuron, endothal, fentin acetate, isoproturon,    methabenzthiazuron, oxyfluorfen, quinoclamine and terbutryn;    Fungicides such as-   benzo[b]thiophenecarboxylic acid cyclohexylamide S,S-dioxide,    dichlofluanid, fluorfolpet, 3-iodo-2-propinyl butylcarbamate,    tolylfluanid and azoles such as azaconazole, cyproconazole,    epoxyconazole, hexaconazole, metconazole, propiconazole and    tebuconazole;    Molluscicides such as-   fentin acetate, metaldehyde, methiocarb, niclosamid, thiodicarb and    trimethacarb; or conventional antifouling active compounds such as-   4,5-dichloro-2-octyl-4-isothiazolin-3-one, diiodomethylparatryl    sulphone, 2-(N,N-dimethylthiocarbamoylthio)-5-nitrothiazyl,    potassium, copper, sodium and zinc salts of 2-pyridinethiol 1-oxide,    pyridine-triphenylborane, tetrabutyldistannoxane,    2,3,5,6-tetrachloro-4-(methylsulphonyl)-pyridine,    2,4,5,6-tetrachloroisophthalonitrile, tetramethylthiuram disulphide    and 2,4,6-trichlorophenylmaleimide.

The antifouling compositions used comprise the active compound accordingto the invention of the compounds according to the invention in aconcentration of 0.001 to 50% by weight, in particular 0.01 to 20% byweight.

Moreover, the antifouling compositions according to the inventioncomprise the customary components such as, for example, those describedin Ungerer, Chem. Ind. 1985, 37, 730–732 and Williams, AntifoulingMarine Coatings, Noyes, Park Ridge, 1973.

Besides the algicidal, fungicidal, molluscicidal active compounds andinsecticidal active compounds according to the invention, antifoulingpaints comprise, in particular, binders.

Examples of recognized binders are polyvinyl chloride in a solventsystem, chlorinated rubber in a solvent system, acrylic resins in asolvent system, in particular in an aqueous system, vinyl chloride/vinylacetate copolymer systems in the form of aqueous dispersions or in theform of organic solvent systems, butadiene/styrene/acrylonitrilerubbers, drying oils such as linseed-oil, resin esters or modifiedhardened resins in combination with tar or bitumens, asphalt and epoxycompounds, small amounts of chlorine rubber, chlorinated polypropyleneand vinyl resins.

If appropriate, paints also comprise inorganic pigments, organicpigments or colorants which are preferably insoluble in salt water.Paints may furthermore comprise materials such as colophonium to allowcontrolled release of the active compounds. Furthermore, the paints maycomprise plasticizers, modifiers which affect the rheological propertiesand other conventional constituents. The compounds according to theinvention or the abovementioned mixtures may also be incorporated intoself-polishing antifouling systems.

The active compounds according to the invention are also suitable forcontrolling animal pests, in particular insects, arachnids and mites,which are found in enclosed spaces such as, for example, dwellings,factory halls, offices, vehicle cabins and the like. They can beemployed in domestic insecticide products for controlling these pestsalone or in combination with other active compounds and auxiliaries.They are active against sensitive and resistant species and against alldevelopment stages.

These pests include:

From the order of the Scorpionidea, for example, Buthus occitanus.

From the order of the Acarina, for example, Argas persicus, Argasreflexus, Bryobia ssp., Dermanyssus gallinae, Glyciphagus domesticus,Ornithodorus moubat, Rhipicephalus sanguineus, Trombicula alfreddugesi,Neutrombicula autumnalis, Dermatophagoides pteronissimus andDermatophagoides forinae.

From the order of the Araneae, for example, Aviculariidae and Araneidae.

From the order of the Opiliones, for example, Pseudoscorpiones chelifer,Pseudoscorpiones cheiridium and Opiliones phalangium.

From the order of the Isopoda, for example, Oniscus asellus andPorcellio scaber.

From the order of the Diplopoda, for example, Blaniulus guttulatus andPolydesmus spp.

From the order of the Chilopoda, for example, Geophilus spp.

From the order of the Zygentoma, for example, Ctenolepisma spp., Lepismasaccharina and Lepismodes inquilinus.

From the order of the Blattaria, for example, Blatta orientalies,Blattella germanica, Blattella asahinai, Leucophaea maderae, Panchloraspp., Parcoblatta, spp., Periplaneta australasiae, Periplanetaamericana, Periplaneta brunnea, Periplarieta fuliginosa and Supellalongipalpa.

From the order of the Saltatoria, for example, Acheta domesticus.

From the order of the Dermaptera, for example, Forficula auricularia.

From the order of the Isoptera, for example, Kalotermes spp. andReticulitermes spp.

From the order of the Psocoptera, for example, Lepinatus spp. andLiposcelis spp.

From the order of the Coleptera, for example, Anthrenus spp., Attagenusspp., Dermestes spp., Latheticus oryzae, Necrobia spp., Ptinus spp.,Rhizopertha dominica, Sitophilus granarius, Sitophilus oryzae,Sitophilus zeamais and Stegobium paniceum.

From the order of the Diptera, for example, Aedes aegypti, Aedesalbopictus, Aedes taeniorhynchus, Anopheles spp., Calliphoraerythrocephala, Chrysozona pluvialis, Culex quinquefasciatus, Culexpipiens, Culex tarsalis, Drosophila spp., Fannia canicularis, Muscadomestica, Phlebotomus spp., Sarcophaga carnaria, Simulium spp.,Stomoxys calcitrans and Tipula paludosa.

From the order of the Lepidoptera, for example, Achroia grisella,Gaileria mellonella, Plodia interpunctella, Tinea cloacella, Tineapellionella and Tineola bisselliella.

From the order of the Siphonaptera, for example, Ctenocephalides canis,Ctenocephalides felis, Pulex irritans, Tunga penetrans and Xenopsyllacheopis.

From the order of the Hymenoptera, for example, Camponotus herculeanus,Lasius fuliginosus, Lasius niger, Lasius umbratus, Monomorium pharaonis,Paravespula spp. and Tetramorium caespitum.

From the order of the Anoplura, for example, Pediculus humanus capitis,Pediculus humanus corporis and Phthirus pubis.

From the order of the Heteroptera, for example, Cimex hemipterus, Cimexlectularius, Rhodinus prolixus and Triatoma infestans.

They are used in the household insecticides sector alone or incombination with other suitable active compounds such as phosphoricesters, carbamates, pyrethroids, growth regulators or active compoundsfrom other known classes of insecticides.

They are used in aerosols, pressure-free spray products, for examplepump and atomizer sprays, automatic fogging systems, foggers, foams,gels, evaporator products with evaporator tablets made of cellulose orpolymer, liquid evaporators, gel and membrane evaporators,propeller-driven evaporators, energy-free, or passive, evaporationsystems, moth papers, moth bags and moth gels, as granules or dusts, inbaits for spreading or in bait stations.

The preparation and the use of the compounds according to the inventionis shown in the examples below.

PREPARATION EXAMPLES Example 1

Trifluoroacetic acid (5 ml) is initially charged at 5° C. A solution oftert-butyl-1-(5-bromo-2-thienyl)₄-(2,6-difluorophenyl)₄-oxobutylcarbamate(II-1) (1.50 g, 3.1 mmol) in dichloromethane (10 ml) is added dropwise.The mixture is allowed to warm to room temperature and stirred at thistemperature for another 3 hours. The liquid phase is concentrated underreduced pressure and the residue is taken up in ethyl acetate (50 ml).The organic solution is washed with 1N aqueous sodium hydroxide solution(50 ml), filtered and concentrated.

This gives 0.85 g (75% of theory) of2-(5-bromo-2-thienyl)-5-(2,6-difluorophenyl)-3,4-dihydro-2H-pyrrole.

HPLC: log P (pH 2.3)=3.45 (93% pure)

NMR (CDCl₃): δ=2.05 (1H, m), 2.57 (1H, m), 3.08 (2H, m), 5.50 (1H, m),6.76 (1H, d), 6.92 (1H, d), 6.97 (2H, m), 73.5 (1H, m) ppm.

The following compounds are obtained analogously to Example 1:

log P No. Compound (pH 2.3) ¹H-NMR(δ in ppm) 2

1.95 (CDCl₃) 1.90(1H, m), 2.55(1H, m),3.01(2H, m), 5.51(1H, m), 7.02(2H,d),7.22(2H, m), 7.42(1H, m), 7.56(1H, m) 3

3.34 (CD₃CN) 1.87(1H, m), 2.69(1H, m),3.08(2H, m), 5.57(1H, m), 6.98(1H,d),7.08(2H, m), 7.34(1H, d), 7.48(1H, m) 4

2.34 5

3.11 (CDCl₃) 2.00(1H, m), 2.63(1H, m),3.07(2H, m), 5.70(1H, m), 6.94(2H,m),7.19–7.37(4H, m), 7.76(1H, d),7.83(1H, d)

Example 6

1.1 g (2.16 mmol) of ethyl5-[1-[(tert-butoxycarbonyl)amino]-4-(2,6-difluorophenyl)-4-oxobutyl]thieno[3,2-b]thiophene-2-carboxylate(II-6) are dissolved in 5 ml of dichloromethane and, at 0° C., are addeddropwise to 15 ml of trifluoroacetic acid. The mixture is stirred at 0°C. for another 30 min, and 100 ml of water are then added. The mixtureis extracted 3 times with dichloromethane. The combined organic phasesare washed twice with water and once with concentrated sodium chloridesolution and dried over sodium sulphate. Using cyclohexane/ethyl acetate(2:1), the mixture is then filtered through a 3 g silica gel cartridgeand the solvent is removed under reduced pressure. The orange oil isrecrystallized from about 20 ml of methyl tert-butyl ketone.

This gives 0.26 g (38% of theory) of ethyl5-[5-(2,6-difluorophenyl)-3,4-dihydro-2H-pyrrol-2-yl]thieno[3,2-b]thiophene-2-carboxylatein the form of slightly yellowish crystals.

m.p.: 107° C.

Example 7

350 mg (0.58 mmol) of tert-butyl4-(2,6-difluorophenyl)-4-oxo-1-{5-[4-(trifluoromethoxythieno[3,2-b]thien-2-yl}butylcarbamate (II-7) are dissolved in 5 ml ofdichloromethane and, at 0° C., added dropwise to a solution of 15 ml ofdichloromethane and 5 ml of trifluoroacetic acid. The reaction mixtureis stirred for 5 min and then stirred into 100 ml of ice-water. Theorganic phase is separated off, the aqueous phase is extracted once withdichloromethane and the organic phases are combined. The organic phaseis once more washed with water, dried over sodium sulphate andconcentrated. The crude product is then purified twice by cartridgechromatography (1. cyclohexane/ethyl acetate-2.dichloromethane/cyclohexane gradient).

This gives 0.077 g (28% of theory) of5-(2,6-difluorophenyl)-2-{5-[4-(trifluoromethoxy)phenyl]thieno[3,2-b]thien-2-yl}-3,4-dihydro-2H-pyrrolein the form of a yellow solid.

m.p.: 135° C.

Starting Materials of the Formula (II)

Example (II-1)

Under an atmosphere of argon, 1,3-difluorobenzene (18.20 g, 0.16 mol)is, at −65° C., initially charged in tetrahydrofuran (100 ml).n-Butyllithium (100 ml, 1.6 M in hexane, 0.16 mol) is added dropwise,and the reaction mixture is stirred at −65° C. for another 30 minutes. Asolution oftert-butyl-2-(5-bromo-2-thienyl)-5-oxo-1-pyrrolidinecarboxylate (IX-1)(41.50 g, 0.12 mol) in tetrahydrofuran (250 ml) is added dropwise, andthe reaction mixture is then allowed to warm to room temperature over aperiod of 16 hours. The reaction mixture is stirred into water (500 ml)and extracted with ethyl acetate (2×400 ml). The combined organic phasesare dried over sodium sulphate, filtered and concentrated.

This gives 45.80 g (76% of theory) of tert-butyl1-(5-bromo-2-thienyl)-4-(2,6-difluorophenyl)-4-oxobutylcarbamate.

HPLC: log P (pH 2.3)=4.29 (95% pure)

NMR (CDCl₃): δ=1.42 (9H, s), 2.26 (2H, m), 2.99 (2H, m), 4.84 (2H, br),6.72 (1H, d), 6.90 (1H, d), 6.96 (2H, m), 7.39 (1H, m) ppm.

The following compounds are obtained analogously to Example (II-1):

log P No. Compound (pH 2.3) ¹H-NMR(δ in ppm) II-2

4.48 (CDCl₃) 1.42(9H, s), 2.31(2H, m),2.99(2H, m), 4.86(1H, br),4.98(1H,br), 6.80–6.95(3H, m),7.15–7.25(3H, m) II-3

4.28 (CD₃CN) 1.36(9H, s), 2.15(2H, m),2.96(2H, m), 4.95(1H, m),5.85(1H,br), 6.90(1H, d), 7.08(2H, m), 7.35(1H, d), 7.51(1H, m) II-4

4.27 II-5

4.20 (CDCl₃) 1.41(9H, s), 2.42(2H, m),3.07(2H, m), 4.80(1H, br),5.15(1H,br), 6.94(2H, m),7.39(4H, m), 7.89(2H, m)

Example (II-6)

Under argon, 0.35 g (3.06, mmol/1.1 eq.) of 1,3-difluorobenzene isdissolved in 20 ml of tetrahydrofuran. At −65° C., 1.2 ml ofbutyllithium solution (23% in hexane) are added dropwise. The reactionmixture is stirred at −30° C. for 10 min. A solution of 1.10 g (2.78mmol) of tert-butyl2-[5-(ethoxycarbonyl)thieno[3,2-b]thien-2-yl]-5-oxo-1-pyrrolidinecarboxylate(IX-6) in 20 ml of tetrahydrofuran is then added dropwise, and themixture is stirred at −20° C. for another 30 min. The mixture is warmedto room temperature and, after 30 min, stirred into 120 ml of cold waterand extracted with methyl tert-butyl ketone. The organic phase is washedin each case once with water and concentrated sodium chloride solution,dried over sodium sulphate and concentrated. The crude product isfiltered through a 3 g silica gel cartridge (mobile phasedichloromethane).

This gives 1.15 g (81% of theory) of ethyl5-[1-[(tert-butoxycarbonyl)amino]-4-(2,6-difluorophenyl)-4-oxobutyl]thieno[3,2-b]thiophene-2-carboxylateas a brown gel.

m.p.: 104° C.

Example (II-7)

Under argon, 184 mg (1.62 mmol/1.1 eq.) of 1,3-difluorobenzene aredissolved in 20 ml of tetrahydrofuran and, at −65° C., 0.7 ml ofbutyllithium solution (23% in hexane) is added dropwise. The mixture isstirred at −30° C. for 10 min. A solution of 710 mg (1.47 mmol) oftert-butyl2-oxo-5-{5-[4-(trifluoromethoxy)phenyl]thieno[3,2-b]thien-2-yl}-1-pyrrolidinecarboxylate(IX-7) in 5 ml of tetrahydrofuran is then added dropwise, and themixture is stirred at −20° C. for 30 mm. The mixture is warmed to roomtemperature and, after 30 min under argon, diluted with 60 ml of waterand extracted with methyl tert-butyl ketone. The organic phase is washedin each case once with water and concentrated sodium chloride solution,dried over sodium sulphate and concentrated. The crude product isfiltered through a 3 g silica gel cartridge using the mobile phasedichloromethane.

This gives 0.24 g (28% of theory) of tert-butyl4-(2,6-difluorophenyl)₄-oxo-1-{5-[4-(trifluoromethoxy)phenyl]thieno[3,2-b]thien-2-yl}butylcarbamateas a yellow solid.

m.p.: 128–130° C.

Starting Materials of the Formula (IX)

Example (IX-1)

At 0° C., 5-(5-bromo-2-thienyl)-2-pyrrolidinone (XI-1) (3.26 g, 94%pure, ≈0.012 mol) is initially charged in dichloromethane (65 ml).Di-tert-butyl dicarbonate (3.00 g, 0.014 mol) and4-dimethylaminopyridine (92 mg, 0.75 mmol) are added successively. Themixture is stirred at room temperature for 24 hours, after which moredi-tert-butyl dicarbonate (0.65 g, 3.0 mmol) and 4-dimethylaminopyridine(10 mg, 0.08 mmol) is added. The mixture is stirred for another 4 hours.The organic solution is washed successively with 1N hydrochloric acid,saturated aqueous sodium bicarbonate solution, water and sodium chloridesolution, dried over sodium sulphate, filtered and concentrated.

This gives 4.10 g (95% of theory) of tert-butyl2-(5-bromo-2-thienyl)-5-oxo-1-pyrrolidinecarboxylate.

HPLC: log P (pH 2.3)=3.03 (96% pure)

m.p.: 93° C.

NMR (CDCl₃): δ=1.43 (9H, s), 2.03–2.09 (1H, m), 2.43–2.58 (2H, m), 2.75(1H, m) 5.37 (1H, m), 6.72 (1H, d), 6.92 (1H, d) ppm.

The following compounds are obtained analogously to Example (IX-1):

No. Compound m.p. log P ¹H-NMR(δ in ppm) IX-2

2.39(pH 2.3) (CDCl₃) 1.39(9H, s), 2.05–2.12(1H, m),2.48–2.58(2H, m),2.77(1H, m)5.47(1H, m), 6.95(2H, m), 7.23(1H, m) IX-3

2.77(pH 7.5) (CDCl₃) 1.36(9H, s), 2.00(1H, m),2.47–2.60(2H, m),2.70–2.80(1H, m)5.55(1H, m), 6.91(1H, d), 7.21(1H, d) IX-4

2.65(pH 2.3) (CDCl₃) 1.36(9H, s), 1.98(1H, m),2.48–2.59(2H, m), 2.77(1H,m)5.55(1H, m), 6.91(1H, d), 7.21(1H, d) IX-5

171° C. 3.03(pH 2.3) (CD₃CN) 1.20(9H, s), 1.93(1H, m),2.45–2.63(3H, m),5.60(1H, m),7.30(1H, s) 7.42(2H, m), 7.82(1H, d),7.95(1H, d)

Example (IX-6)

Under argon, 2.00 g (6.77 mmol) of ethyl5-(5-oxo-2-pyrrolidinyl)thieno[3,2-b]thiophene-2-carboxylate (XI-6) aredissolved in 40 ml of dichloromethane and, at 0° C., 3.00 g (13.7 mmol/2eq.) of di-tert-butyl dicarbonate, 0.84 g (6.9 mmol/1.02 eq.) of4-dimethylaminopyridine and 9.0 ml of triethylamine are addedsuccessively. The mixture is stirred at 0° C. for 60 min. The mixture isdiluted with 60 ml of dichloromethane, washed twice with in each case100 ml of aqueous hydrochloric acid (0.25 N), once with water and oncewith concentrated sodium chloride solution, dried over sodium sulphateand concentrated. At about 40° C., the crude product is then stirred in10 ml of methyl tert-butyl ketone, filtered off with suction and dried.

This gives 2.3 g (86% of theory) of tert-butyl2-[5-(ethoxycarbonyl)thieno[3,2-b]thien-2-yl]-5-oxo-1-pyrrolidinecarboxylateas a light-brown solid.

m.p.: 178° C.

Example (IX-7)

Under argon, 6.6 g (8.94 mmol, 52% pure) of5-{5-[4-(trifluoromethoxy)phenyl]thieno[3,2-b]thien-2-yl}-2-pyrrolidinone(XI-7) are dissolved in 120 ml of dichloromethane, and 7.5 g (34.2mmol/2, eq.) of di-tert-butyl dicarbonate, 2.2 g (17.5 mmol/1.02 eq.) of4-dimethylaminopyridine and 23 ml of triethylamine are addedsuccessively at 0° C. The mixture is stirred at 0° C. for another 2hours. The mixture is diluted with 60 ml of dichloromethane, washedtwice with in each case 50 ml of aqueous hydrochloric acid (0.25 N),once with water and once with concentrated sodium chloride solution andthen dried over sodium sulphate. The resulting solution is filteredthrough silica gel using dichloromethane and the solvent is thenremoved.

This gives 4.1 g (95% of theory) of tert-butyl2-oxo-5-{5-[4-(trifluoromethoxy)phenyl]thieno[3,2-b]thien-2-yl)-1-pyrrolidinecarboxylatein the form of a grey solid.

m.p.: 164° C.

Starting Materials of the Formula (XI)

Example (XI-1)

A mixture of glacial acetic acid (15 ml) and concentrated sulphuric acid(5 ml) is initially charged and cooled to 0° C.5-Ethoxy-pyrrolidin-2-one (3.04 g, 85% pure, 0.02 mol) and2-bromothiophene (13.12 g, 0.08 mol) are added successively. Thereaction mixture is allowed to slowly warm to room temperature and thenstirred at this temperature for 60 hours. The mixture is poured intoice-water and extracted with ethyl acetate. The organic phase is washedsuccessively with saturated aqueous sodium bicarbonate solution, waterand sodium chloride solution, dried over sodium sulphate, filtered andconcentrated.

This gives 3.94 g (75% of theory) of5-(5-bromo-2-thienyl)-2-pyrrolidinone.

HPLC: log P (pH 2.3)=1.62 (94% pure)

m.p.: 104° C.

NMR (CDCl₃): δ=2.10 (1H, m), 2.34–2.66 (3H, m), 4.94 (1H, m), 6.01 (1H,br), 6.75 (1H, d), 6.91 (1H, d) ppm.

The following compounds are obtained analogously to Example (IX-1):

m.p. log P No. Compound (° C.) (pH 2.3) ¹H-NMR(δ in ppm) XI-2

111 1.03 (CDCl₃) 2.14(1H, m), 2.36–2.63(3H, m),5.04(1H, m), 6.15(1H,br), 6.98(2H, m),7.26(1H, m) XI-3

122 1.41 (CDCl₃) 2.14(1H, m), 2.38–2.73(3H, m),5.16(1H, m), 6.00(1H,br), 6.91(1H, d),7.25(1H, d) XI-4

104 1.33 (CDCl₃) 2.12(1H, m), 2.44–2.60(3H, m),5.10(1H, m), 6.15(1H,br), 6.81(1H, d),7.25(1H, d) XI-5

115 1.73 (CD₃CN) 2.03(1H, m), 2.33(2H, m),2.66(1H, m), 5.14(1H, m),6.45(1H, br),7.42(3H, m), 7.83(1H, d), 7.94(1H, d)

Example (XI-6)

1.2 g (9.42 mmol) of 5-ethoxy-2-pyrrolidinone are initially charged in15 ml of glacial acetic acid and 5 ml of concentrated sulphuric acid. Ata temperature below 10° C., 1.0 g (4.71 mmol) of ethylthieno[3,2-b]thiophene-2-carboxylate is added, and the mixture isstirred at room temperature for another 40 h. The mixture is stirredinto 150 ml of cold water and extracted three times with in each case 25ml of dichloromethane. The combined organic phases are washed twice withwater and once with concentrated sodium chloride solution, dried andconcentrated. The yellow crude product is stirred in about 20 ml ofmethyl tert-butyl ketone. The residue is filtered off with suction anddried.

This gives 1.0 g (72% of theory) of ethyl5-(5-oxo-2-pyrrolidinyl)thieno[3,2-b]thiophene-2-carboxylate in the formof cream-coloured crystals.

m.p.: 140° C.

Example (XI-7)

5.3 g (40.6 mmol) of 5-ethoxy-2-pyrrolidinone are initially charged in80 ml of glacial acetic acid and 27 ml of concentrated sulphuric acid.At a temperature below 10° C., 6.1 g (20.3 mmol) of2-[4-(trifluoromethoxy)-phenyl]thieno[3,2-b]thiophene (XIII-1) areadded, and the mixture is stirred at room temperature for another 16hours. The mixture is stirred into 300 ml of cold water and extractedthree times with in each case 60 ml of dichloromethane. The organicphases are combined, washed twice with water and once with concentratedsodium chloride solution, dried over sodium sulphate and concentrated.The crude product is then stirred in 60 ml of methyl tert-butyl ketoneat about 40° C., cooled, filtered off with suction and dried.

This gives 6.8 g (87% of theory) of5-{5-[4-(trifluoromethoxy)phenyl]thieno[3,2-b]thien-2-yl}-2-pyrrolidinoneas a light-grey solid.

m.p.: 220° C. (decomposition)

Starting Materials of the Formula (XIII)

Example (XIII-1)

Under argon, 29.0 g (25.5 mmol) of 2-bromothien[3,2-b]thiophene-aredissolved in 150 ml of tetrahydrofuran, 10.0 g (48.5 mmol) of4-trifluoromethoxyphenylboronic acid and 0.8 g (0.7 mmol) oftetrakis(triphenylphosphine)-palladium(0) are added at room temperatureand the mixture is heated at reflux for 1 hour. Another 2.0 g of4-trifluoromethoxyphenylboronic acid and 0.2 gtetrakis(triphenylphosphine)-palladium(0) are then added, and themixture is stirred at reflux for another 16 hours.

At this temperature, a total of 100 ml of a 20% strength aqueous sodiumcarbonate solution are then added dropwise, and the mixture is heated atreflux for 1 hour. The reaction mixture is diluted with 400 ml of waterand extracted three times with in each case 100 ml of methyl tert-butylketone. The organic phases are combined, washed in each case once withwater and concentrated sodium chloride solution, dried over sodiumsulphate and concentrated. The crude product is absorbed on about 25 gof silica gel and purified by flash chromatography using the mobilephase n-hexane.

This gives 6.2 g (81% of theory) of2-[4-(trifluoromethoxy)phenyl]thieno[3,2-b]thiophene in the form of awhite solid.

m.p.: 162° C.

Example 8

4-Azido-4-(4-bromo-2-thienyl)-1-(2,6-difluorophenyl)-1-butanone (III-1)(1.63 g, 42% pure, ≈1.79 mmol) is initially charged in n-pentane (100ml). At room temperature, triphenylphosphine (0.65 g, 2.50 mmol) isadded a little at a time. The mixture is stirred at room temperature foranother 16 hours. Florisil (5 g) is added, and the mixture isconcentrated to dryness. The crude product is purified by silica gelchromatography (mobile phase: cyclohexane/ethyl acetate 9:1→7:3).

This gives 0.15 g (37% of theory) of2-(4-bromo-2-thienyl)-5-(2,6-difluorophenyl)-3,4-dihydro-2H-pyrrole.

HPLC: log P (pH 2.3)=3.41 (100% pure)

NMR (CD₃CN): δ=1.95 (1H, m), 2.60 (1H, m), 3.05–3.08 (2H, m), 5.47 (1H,m), 6.96 (1H, s), 7.07 (2H, m), 7.27 (1H, s), 7.44–7.47 (1H, m) ppm.

A further batch (0.15 g, 78% pure) was also isolated.

Example 9

4-Azido-4-(6-chloro-3-pyridinyl)-1-(2,6-difluorophenyl)-1-butanone(III-2) (1.20 g, 54.4% pure, 1.94 mmol) is initially charged in n-hexane(100 ml). At room temperature, triphenylphosphine (0.94 g, 3.56 mmol) isadded a little at a time. The mixture is stirred at room temperature foranother 16 hours. Florisil (7 g) is added, and the reaction mixture isthen evaporated to dryness. The crude product is purified by silica gelchromatography (mobile phase: cyclohexane/ethyl acetate 9:1→7:3).

This gives 0.47 g (83% of theory) of2-(6-chloro-3-pyridinyl)-5-(2,6-difluorophenyl)-3,4-dihydro-2H-pyrrole.

HPLC: log P (pH 2.3)=1.93 (100% pure)

NMR (CD₃CN): δ=1.77–1.84 (1H, m), 2.60–2.66 (1H, m), 3.05–3.09 (2H, m),5.32 (1H, m), 7.07 (2H, m), 7.38 (1H, d), 7.47 (1H, m), 7.69 (1H, dd),8.37 (1H, d) ppm.

Example 10

4-Azido-1-(2,6-difluorophenyl)-4-{6-[4-(trifluoromethoxy)phenyl]-3-pyridinyl}-1-butanone(1-3) (0.80 g, 1.73 mmol) is initially charged in n-hexane (100 ml).

Triphenylphosphine (0.45 g, 1.73 mmol) is added. The mixture is stirredat room temperature for another 16 hours. Florisil (5 g) is added, andthe reaction mixture is concentrated. The crude product is purified bysilica gel chromatography (mobile phase: hexane/ethyl acetate 9:1→4:1).

This gives 0.42 g (50% of theory) of5-[5-(2,6-difluorophenyl)-3,4-dihydro-2H-pyrrol-2-yl]-2-[4-(trifluoromethoxy)phenyl]pyridine.

HPLC: log P (pH 2.3)=3.50 (86% pure)

Starting Materials of the Formula (III)

Example (III-1)

4-(4-Bromo-2-thienyl)-4-chloro-1-(2,6-difluorophenyl)-1-butanone (XV-1)(0.95 g, 84.65% pure, ≈2.1 mmol) is initially charged in acetone (4 ml).A solution of sodium azide (0.25 g, 3.75 mmol) in water (10 ml) andmethyl-tri-n-octylammonium chloride (0.30 g, 0.74 mmol) are addedsuccessively. The mixture is stirred at 50° C. for another 16 hours.Water (30 ml) is added, and the reaction mixture is extracted with ethylacetate (2×50 ml). The combined organic phases are dried over sodiumsulphate, filtered and concentrated. The crude product is reactedfurther without any purification.

This gives 1.63 g (85% of theory) of4-azido-4-(4-bromo-2-thienyl)-1-(2,6-difluorophenyl)-1-butanone.

HPLC: log P (pH 2.3)=3.00 (42% pure)

{tilde over (ν)}_(azide): 2090 cm⁻¹

Example (III-2)

4-(6-Chloro-3-pyridinyl)-4-chloro-1-(2,6-difluorophenyl)-1-butanone(XV-2) (1.30 g, 57.6% pure, 2.27 mmol) is initially charged in acetone(7.5 ml). A solution of sodium azide (0.38 g, 5.90 mmol) in water (15ml) and methyl tri-n-octylammonium chloride (0.30 g, 0.74 mmol) areadded successively. The mixture is stirred at 50° C. for another 16hours. Water (30 ml) is added, and the reaction mixture is extractedwith ethyl acetate (2×50 ml). The combined organic phases are dried oversodium sulphate, filtered and concentrated. The crude product is reactedfurther without any purification.

This gives 1.20 g (85% of theory) of4-azido-4-(6-chloro-3-pyridinyl)-1-(2,6-difluorophenyl)-1-butanone.

HPLC: log P (pH 2.3)=3.33 (54% pure)

{tilde over (ν)}_(azide): 2080 cm⁻¹

Example (III-3)

4-Chloro-1-(2,6-difluorophenyl)-4-{6-[4-(trifluoromethoxy)phenyl]-3-pyridinyl}-1-butanone(XV-3) (0.81 g, 1.78 mmol) is initially charged in acetone (5 ml). Asolution of sodium azide (0.17 g, 2.67 mmol) in water (10 ml) andmethyl-tri-n-octylammonium chloride are added successively. The mixtureis stirred at 50° C. for another 16 hours. Water is added, and thereaction mixture is extracted twice with ethyl acetate. The combinedorganic phases are dried over sodium sulphate, filtered andconcentrated.

This gives 0.80 g (61% of theory) of4-azido-1-(2,6-difluorophenyl)-4-{6-[4-(trifluoromethoxy)phenyl]-3-pyridinyl}-1-butanone.

HPLC: log P (pH 2.3)=4.78 (63% pure)

Starting Materials of the Formula (XV).

Example (XV-1)

At room temperature,[2-(4-bromo-2-thienyl)cyclopropyl](2,6-difluorophenyl)methanone (XVII-1)(1.40 g, 82% pure, ≈3.4-mmol) is stirred with concentrated hydrochloricacid (10 ml) for 72 hours. Dichloromethane is added, and the organicphase is washed with water, dried over sodium sulphate, filtered andconcentrated. The crude product is reacted further without anypurification.

This gives 1.27 g (83% of theory) of4-(4-bromo-2-thienyl)₄-chloro-1-(2,6-difluorophenyl)-1-butanone.

HPLC: log P (pH 2.3)=3.00 (85% pure)

NMR (CD₃CN): δ=2.48 (2H, m), 3.08 (2H, m), 5.36 (1H, m), 7.00–7.12 (3H,m 7.40 (1H, s), 7.47–7.57 (1H, m) ppm.

Example (XV-2)

At room temperature,[2-(6-chloro-3-pyridinyl)cyclopropyl](2,6-difluorophenyl)methanone(XVII-2) (2.20 g, 7.50 mmol) is stirred with concentrated hydrochloricacid (22 ml) for 60 hours. The reaction mixture is concentrated underreduced pressure. The crude product is reacted further without anypurification.

This gives 2.10 g (49% of theory) of4-(6-chloro-3-pyridinyl)-4-chloro-1-(2,6-difluorophenyl)-1-butanone.

HPLC: log P (pH 2.3)=3.37 (58% pure)

Example (XV-3)

At room temperature,(2,6-difluorophenyl)(2-{6-[4-(trifluoromethoxy)phenyl]-3-pyridinyl}cyclopropyl)methanone(XVII-3) (0.75 g, 1.79 mmol) is stirred with concentrated hydrochloricacid (8.00 ml) for 60 hours. The reaction mixture is concentrated underreduced pressure.

This gives 0.81 g (85% of theory) of4-chloro-1-(2,6-difluorophenyl)₄-{6-[4-(trifluoromethoxy)phenyl]-3-pyridinyl}-1-butanone.

HPLC: log P (pH 2.3)=4.88 (86% pure)

Starting Materials of the Formula (XVII)

Example (XVII-1)

Sodium hydride (0.40 g, 0.01 mol, 60% suspension in paraffin oil) issuspended in DMSO (15 ml). At room temperature, trimethylsulphoxoniumiodide (2.20 g, 0.01 mol) is added a little at a time. The reactionmixture is then stirred at room temperature for 0.5 hours. At roomtemperature, a solution of 3-(4-bromo-2-thienyl)-1-(2,6-difluorophenyl)-2-propen-1-one (XVII-1) (2.30 g, 7.0 mmol) indimethyl sulphoxide (15 ml) is slowly added dropwise, and the mixture isthen stirred at room temperature for another 16-hours. The mixture ispoured into ice-water and extracted twice with ethyl acetate. Thecombined organic phases are dried over sodium sulphate, filtered andconcentrated. The crude product is reacted further without anypurification.

This gives 1.86 g (63% of theory) of[2-(4-bromo-2-thienyl)cyclopropyl](2,6-difluorophenyl)methanone.

HPLC: log P (pH 2.3)=4.14 (82.0% pure)

NMR (CD₃CN): δ=1.59 (1H, m), 1.87 (1H, m), 2.73 (1H, m), 2.84 (1H, m),6.88 (1H, s), 7.08 (2H, m), 7.19 (1H, s), 7.54 (1H, m) ppm.

Example (XVII-2)

Sodium hydride (3.19 g, 79.84 mmol, 60% suspension in paraffin oil) issuspended in dimethyl sulphoxide (100 ml). At a temperature at or below32° C., trimethylsulphoxonium iodide (17.57 g, 79.84 mmol) is added alittle at a time. The reaction mixture is then stirred at roomtemperature for another 1.5 hours. A solution of3-(6-chloro-3-pyridinyl)-1-(2,6-difluorophenyl)-2-propen-1-one (XVIII-2)(20.30 g, 72.59 mmol) in DMSO (120 ml) is slowly added dropwise at atemperature of 36° C. or below. The mixture is then stirred at roomtemperature for another 16 hours. The reaction mixture is poured intoice-water and the precipitate is filtered off with suction.

This gives 22.70 g (97% of theory) of[2-(6-chloro-3-pyridinyl)cyclopropyl](2,6-difluorophenyl)methanone.

HPLC: log P (pH 2.3)=2.92 (91% pure)

NMR (CD₃CN): δ=1.63 (1H, m), 1.91 (1H, m), 2.73 (2H, m), 7.07 (2H, m),7.32 (2H, d), 7.50–7.55 (3H, m), 8.28 (1H, d) ppm.

Example (XVII-3)

4,4,5,5-Tetramethyl-2-[4-(trifluoromethoxy)phenyl]-1,3,2-dioxaborolane(1.73 g, 6.00 mmol), bis(diphenylmethylphosphine)palladium(II) chloride(0.11 g, 0.15 mmol) and sodium carbonate solution (7.50 ml, 2 M) areadded successively to a solution of[2-(6-chloro-3-pyridinyl)cyclopropyl](2,6-difluorophenyl)methanone(XVII-2) (1.47 g, 5.00 mmol) in 20 ml of dimethoxyethane, and thereaction mixture is then allowed to react at 80° C. for 16 hours. Forwork-up, water is added to the reaction mixture and the resultingprecipitate is filtered off with suction. The precipitate is taken up indichloromethane, 10 g of Florisil are added and the mixture is thenpurified by silica gel chromatography (mobile phase: hexane/ethylacetate 9:1, v/v).

This gives 1.09 g (51% of theory) of(2,6-difluorophenyl)(2-{6-[4-(trifluoromethoxy)phenyl]-3-pyridinyl}cyclopropyl)methanone.

HPLC: log P (pH 2.3)=4.40 (98% pure)

Starting Materials of the Formula (XVIII)

Example (XVIII-1)

2,6-Difluoroacetophenone (1.56 g, 0.01 mol) and4-bromothiophene-2-carboxaldehyde (1.91 g, 0.01 mol) are initiallycharged in methanol (70 ml) and, water (16 ml). At room temperature,aqueous sodium hydroxide solution (3 ml, 10% w/v) is added dropwise, andthe mixture is then stirred at room temperature for another 16 hours.After cooling to 0° C., the precipitate is filtered off with suction andwashed with an ice-cold methanol/water (3:1) mixture.

This gives 2.49 g (76% of theory) of3-(4-bromo-2-thienyl)-1-(2,6-difluorophenyl)-2-propen-1-one.

HPLC: log P (pH 2.3)=3.78 (100% pure)

NMR (CD₃CN): δ=6.89 (1H, d), 7.11 (2H, m), 7.40 (1H, s), 7.54–7.59 (3H,m) ppm.

Example (XVIII-2)

2,6-Difluoroacetbphenone (15.60 g, 0.10 mol) and2-chloropyridine-5-carboxaldehyde (14.20 g, 0.10 mol) are initiallycharged in methanol (300 ml) and water (100 ml). At 5–8° C., aqueoussodium hydroxide solution (30 ml, 10% w/v) is slowly added dropwise. Thereaction mixture is then stirred at 8° C. for one hour. The precipitateis filtered off with suction.

This gives 20.30 g (73% of theory) of3-(6-chloro-3-pyridinyl)-1-(2,6-difluorophenyl)-2-propen-1-one.

HPLC: log P (pH 2.3)=2.87 (98.54% pure)

NMR (CD₃CN): δ=7.09–7.20 (3H, m), 7.45–7.61 (3H, m), 8.04 (1H, dd), 8.58(1H, d) ppm.

Example 11

Under an atmosphere of argon,2-(5-bromo-2-thienyl)-(2,6-difluorophenyl)-3,4-dihydro-2H-pyrrole(Ex. 1) (0.65 g, 1.90 mmol) and 4-trifluoromethoxyphenylboronic acid(0.50 g, 2.4 mmol) are initially charged in acetone (10 ml). A solutionof potassium carbonate (0.70 g, 5.07 mmol) in water (10 ml) and asolution of palladium acetate (13 mg, 0.058 mmol) in acetone (2 ml) areadded successively. The mixture is stirred at 60° C. for 4 hours, more4-trifluoromethoxyphenylboronic acid (0.25 g, 1.2 mmol), of the solutionof potassium carbonate (0.35 g, 2.37 mmol) in water (5 ml) and of thesolution of palladium acetate (6 mg, 0.027 mmol) in acetone (1 ml) areadded, and the mixture is stirred at 60° C. for another 6 hours. Aftercooling to room temperature, the mixture is filtered and concentrated.The filtrate is diluted with ethyl acetate and water and the phases areseparated. The organic phase is dried over sodium sulphate, filtered andconcentrated. The crude product is purified by silica gel chromatography(mobile phase: cyclohexane/ethyl acetate 4:1).

This gives 0.40 g (47% of theory) of5-(2,6-difluorophenyl)-2-{5-[4-(trifluoromethoxy)phenyl]-2-thienyl}-3,4-dihydro-2H-pyrrole.

HPLC: log P (pH 2.3)=5.16(95% pure)

NMR (CD₃CN): δ=2.12 (1H, m), 2.62 (1H, m), 3.08 (1H, m), 3.14 (1H, m),5.58 (1H, m), 6.97 (3H, m), 7.15 (1H, s), 7.20 (2H, d), 7.34 (1H, m),7.58 (2H, d) ppm.

Example 12

Under an atmosphere of argon,2-(5-bromo-2-thienyl)-(2,6-difluorophenyl)-3,4-dihydro-2H-pyrrole(Ex. 1) (0.65 g, 1.90 mmol) and 3-trifluoromethoxyphenylboronic acid(0.50 g, 2.4 mmol) are initially charged in acetone (10 ml). A solutionof potassium carbonate (0.70 g, 5.07 mmol) in water (10 ml) and asolution of palladium acetate (26 mg, 0.12 mmol) in acetone (3 ml) areadded successively. The reaction mixture is stirred at 60° C. for 16hours. After cooling to room temperature, the mixture is diluted withethyl acetate and water and the phases are separated. The organic phaseis dried over sodium sulphate, filtered and concentrated. The crudeproduct is purified by silica gel chromatography (mobile phase:cyclohexane/ethyl acetate 9:1).

This gives 0.45 g (53% of theory) of5-(2,6-difluorophenyl)-2-{5-[3-(trifluoromethoxy)phenyl]-2-thienyl}-3,4-dihydro-2H-pyrrole.

HPLC: log P (pH 2.3)=4.84 (94% pure)

NMR (CD₃CN): δ=2.15 (1H, m), 2.65 (1H, m), 3.13 (2H, m), 5.61 (1H, m),6.99 (3H, m), 7.11 (1H, m), 7.22 (1H, d), 7.33–7.49 (3H, m), 7.51 (1H,m) ppm.

Example 13

Under an atmosphere of argon,2-(4-bromo-2-thienyl)-5-(2,6-difluorophenyl)-3,4-dihydro-2H-pyrrole (Ex.8) (0.56 g, 1.70 mmol) and 3-trifluoromethoxyphenylboronic acid (0.50 g,2.4 mmol) are initially charged in acetone (10 ml). A solution ofpotassium carbonate (0.70 g, 5.07 mmol) in water (10 ml) and a solutionof palladium acetate (24 mg, 0.11 mmol) in acetone (3 ml) are addedsuccessively. The reaction mixture is stirred at 60° C. for 16 hours.After cooling to room temperature, the mixture is diluted with ethylacetate and water and the phases are separated. The organic phase isdried over sodium sulphate, filtered and concentrated. The crude productis purified by silica gel chromatography (mobile phase: toluene/ethylacetate 1:0 e 9:1).

This gives 0.41 g (53% of theory) of5-(2.6-difluorophenyl)-2-{4-[3-(trifluoromethoxy)phenyl]-2-thienyl}-3,4-dihydro-2H-pyrrole.

HPLC: log P (pH 2.3)=4.08 (93.6% pure)

NMR (CD₃CN): δ=2.05 (1H, m), 2.64 (1H, m), 3.07 (2H, m), 5.54 (1H, m),7.07 (2H, m), 7.23 (1H, d), 7.39 (1H, s), 7.51 (2H, m), 7.58 (2H, m),7.67 (1H, d) ppm.

Example 14

Under an atmosphere of argon,2-(4-bromo-2-thienyl)-5-(2,6-difluorophenyl)-3,4-dihydro-2H-pyrrole (Ex.8) (0.75 g, 2.30 mmol) and 4-trifluoromethoxyphenylboronic acid (0.71 g,3.45 mmol) are initially charged in acetone (10 ml). A solution ofpotassium carbonate (0.75 g, 5.43 mmol) in water (10 ml) and a solutionof palladium acetate (25 mg, 0.11 mmol) in acetone (3 ml) are addedsuccessively. The reaction mixture is stirred at 60° C. for 16 hours.After cooling to room temperature, the mixture is diluted with ethylacetate and water and the phases are separated. The organic phase isdried over sodium sulphate, filtered and concentrated. The crude productis purified by silica gel chromatography (mobile phase: n-hexane/ethylacetate 9:1).

This gives 0.15 g (15% of theory) of5-(2,6-difluorophenyl)-2-{4-[4-(trifluoromethoxy)phenyl]-2-thienyl}-3,4-dihydro-2H-pyrrole.

HPLC: log P (pH 2.3)=4.66 (96.3% pure)

NMR (CD₃CN): δ=2.05 (1H, m), 2.65 (1H, m), 3.07 (2H, m), 5.54 (1H, m),7.08 (2H, m), 7.33 (2H, d), 7.37 (1H, s), 7.47 (1H, m), 7.49 (1H, s),7.73 (2H, d) ppm.

The stated logP values were determined in accordance with EEC Directive79/831 Annex V.A8 by HPLC (High Performance Liquid Chromatography),using a reversed-phase column (C 18). Temperature: 43° C.

In the acidic range, the determination was carried out at pH 2.3 usingthe mobile phases 0.1% aqueous phosphoric acid and acetonitrile; lineargradient from 10% acetonitrile to 90% acetonitrile.

In the neutral range, the determination was carried out at pH 7.5 usingthe mobile phases 0.01 molar aqueous phosphate buffer solution andacetonitrile; linear gradient from 10% acetonitrile to 90% acetonitrile.

Calibration was carried out using unbranched alkan-2-ones (having 3 to16 carbon atoms) with known logP values (determination of the logPvalues by the retention times using linear interpolation between twosuccessive alkanones).

The lambda-max values were determined in the maxima of thechromatographic signals using the UV spectra from 200 nm to 400 nm.

USE EXAMPLES Example A

Meloidogyne Test

-   Solvent: 30 parts by weight of dimethylformamide-   Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent andemulsifier, and the concentrated is diluted with water to the desiredconcentration.

Vessels are filled with sand, solution of active compound, Meloidogyneincognita egg/larvae suspension and lettuce seeds. The lettuce seedsgerminate and the plants develop. On the roots galls are formed.

After the desired period of time, the nematicidal action is determinedin % by the formation of galls. 100% means that no galls have beenfound; 0% means that the number of galls on the treated plantscorresponds to that of the untreated control.

Active compounds and test results are shown in the Table below.

TABLE A plant-damaging nematodes Meloidogyne Test Concentration ofactive Kill rate Active compounds compound in ppm in % after 14 d

20 98

Example B

Myzus Test

-   Solvent: 7 parts by weight of dimethylformamide-   Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Cabbage leaves (Brassica oleracea) which are heavily infested by thepeach aphid (Myzus persicae) are treated by being dipped into thepreparation of active compound of the desired concentration.

After the desired period of time, the kill in % is determined. 100%means that all aphids have been killed; 0% means that none of the aphidshave been killed.

Active compounds and test results are shown in the Table below.

TABLE B plant-damaging insects Myzus Test Concentration of active Killrate Active compounds compound in ppm in % after 6^(d)

1000 95

Example C

Phaedon Larvae Test

-   Solvent: 30 parts by weight of dimethylformamide-   Emulsifier: 1 part by weight of alkylaryl polyglycol ether To    produce a suitable preparation of active compound, 1 part by weight    of active compound is mixed with the stated amount of solvent and    emulsifier, and the concentrate is diluted with    emulsifier-containing water to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of active compound of the desired concentration and arepopulated with larvae of the mustard beetle (Phaedon cochleariae) whilethe leaves are still moist.

After the desired period of time, the kill in % is determined. 100%means that all beetle larvae have been killed; 0% means that none of thebeetle larvae have been killed.

Active compounds and test results are shown in the Table below.

TABLE C plant-damaging insects Phaedon Larvae Test Concentration ofactive Kill rate Active compounds compound in ppm in % after 7^(d)

1000 100

1000 100

1000 100

Example D

Plutella Test

-   Solvent: 30 parts by weight of dimethylformamide-   Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of active compound of the desired concentration and arepopulated with caterpillars of the diamond back moth (Plutellaxylostella) while the leaves are still moist.

After the desired period of time, the kill in % is determined. 100%means that all caterpillars have been killed; 0% means that none of thecaterpillars have been killed.

Active compounds and test results are shown in the Table below.

TABLE D plant-damaging insects Plutella test Concentration of activeKill rate Active compounds compound in ppm in % after 6^(d)

8 90

Example E

Spodoptera frugiperda Test

-   Solvent: 30 parts by weight of dimethylformamide.-   Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of active compound of the desired concentration and arepopulated with caterpillars of the army worm (Spodoptera frugiperda)while the leaves are still moist.

After the desired period of time, the kill in % is determined. 100%means that all caterpillars have been killed; 0% means that none of thecaterpillars have been killed.

Active compounds and test results are shown in the Table below.

TABLE E plant-damaging insects Spodoptera frugiperda Test Concentrationof active Kill rate Active compounds compound in ppm in % after 7^(d)

500 100

1000 100

1000 100

1000 100

1000 100

500 100

Example F

Tetranychus Test (OP-Resistent/Dip Treatment)

-   Solvent: 30 parts by weight of dimethylformamide-   Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Bean plants (Phaseolus vulgaris) which are heavily infested by allstages of the greenhouse red spider mite (Tetranychus urticae) aredipped into a preparation of active compound of the desiredconcentration.

After the desired period of time, the effect in % is determined. 100%means that all spider mites have been killed; 0% means that none of thespider mites have been killed.

Active compounds and tests results are shown in the Table below.

TABLE F plant-damaging mites Tetranychus Test (OP-resistent/diptreatment) Concentration of active Kill rate Active compounds compoundin ppm in % after 7^(d)

500 80

Example G

Diabrotica balteata Test (Larvae in Soil)

Critical Concentration Test/Soil Insects—Treatment of Transgenic Plants

-   Solvent: 7 parts by weight of dimethylformamide-   Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, thestated amount of emulsifier is added and the concentrate is diluted withwater to the desired concentration.

The preparation of active compound is poured onto the soil. Here, theconcentration of the active compound in the preparation is virtuallyimmaterial, only the amount by weight of active compound per volume unitof soil, which is stated in ppm (mg/l), matters. The soil is filled into0.25 l pots, and these are allowed to stand at 20° C.

Immediately after the preparation, 5 pregerminated maize corns of thecultivar YIELD GUARD (trademark of Monsanto Comp., USA) are placed intoeach pot.

After 2 days, the corresponding test insects are placed into the treatedsoil. After a further 7 days, the efficacy of the active compound isdetermined by counting the number of maize plants that have emerged (1plant=20% activity).

Example H

Heliothis virescens Test (Treatment of Transgenic Plants)

-   Solvent: 7 parts by weight of dimethylformamide-   Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Soyabean shoots (Glycine max) of the cultivar Roundup Ready (trademarkof Monsanto Comp. USA) are treated by being dipped into the preparationof active compound of the desired concentration and are populated withthe tobacco bud worm caterpillar Heliothis virescens while the leavesare still moist.

After the desired period of time, the kill in % is determined. 100%means that all caterpillars have been killed; 0% means that none of thecaterpillars have been killed.

1. A Δ¹ pyrroline of the Formula (I)

in which R¹ represents halogen, in each case optionally substitutedalkyl or alkoxy or —S(O)_(w)R⁴, R² and R³ independently of one anotherrepresent hydrogen, halogen or in each case optionally substitutedalkyl, alkoxy or alkoxyalkyl, R⁴ represents optionally substitutedalkyl, Het represents heteroaryl which is optionally mono- orpolysubstituted by identical or different R⁵, R⁵ represents the grouping—X—Y-Z-E with the proviso that Y does not represent a direct bond if Xdoes not represent a direct bond, X represents a direct bond, oxygen,—S(O)_(w)—, —NR⁶—, carbonyl, carbonyloxy, oxycarbonyl, oxysulphonyl(OSO₂), alkylene, halogenalkylene, alkenylene, halogenoalkenylene,alkinylene, alkyleneoxy, oxyalkylene, oxyalkyleneoxy,—S(O)_(w)-alkylene, cyclopropylene or oxiranylene, Y represents a directbond or represents in each case optionally substituted phenylene,naphthylene, tetrahydronaphthylene or heterocyclylene, Z represents adirect bond or —(CH₂)_(n)—, E represents hydrogen, halogen, hydroxyl,cyano, formyl, nitro, trialkylsilyl, pentafluorothio, —S(O)_(w)R⁷,—OSO₂R⁷, —NR⁸R⁹, —COR⁷, —CO₂R⁷, —OC(O)R⁷, —CONR¹⁰R¹¹, —N(R¹²)COR¹³,—C(R¹⁴)═N—OR¹⁵, —SO₂NR¹⁶R¹⁷; represents in each case optionallysubstituted alkyl, alkenyl, alkinyl, alkoxy, alkenyloxy, cycloalkyl,cycloalkylalkyl, cycloalkyloxy, aryl, arylalkyl, aryloxy, aryloxyalkyl,saturated or unsaturated heterocyclyl or heterocyclylalkyl, R⁶represents in each case optionally substituted alkyl, cycloalkyl,cycloalkylalkyl, aryl or arylalkyl, R⁷ represents in each caseoptionally substituted alkyl, cycloalkyl, aryl or arylalkyl, R⁸ and R⁹independently of one another represent hydrogen, —SO₂R⁷, —COR⁷, —CO₂R⁷,represent in each case optionally substituted alkyl, alkenyl,cycloalkyl, cycloalkylalkyl, aryl, arylalkyl or saturated or unsaturatedheterocyclyl or heterocyclylalkyl, or R⁸ and R⁹ furthermore togetherrepresent in each case optionally substituted alkenylene or alkylene,where the alkylene chain may in each case be interrupted by —O—, —S— or—NR¹⁸—, R¹⁰ and R¹¹ independently of one another represent hydrogen,—SO₂R⁷, represent in each case optionally substituted alkyl, alkenyl,cycloalkyl, cycloalkylalkyl, aryl, arylalkyl or saturated or unsaturatedheterocyclyl or heterocyclylalkyl, or R¹⁰ and R¹¹ furthermore togetherrepresent optionally substituted alkylene, where the alkylene chain mayin each case be interrupted by —O—, —S— or —NR¹⁸—, R¹² and R¹³independently of one another represent hydrogen, represent in each caseoptionally substituted alkyl, cycloalkyl, cycloalkylalkyl, aryl orarylalkyl, or R¹² and R¹³ furthermore together represent in each caseoptionally substituted alkylene or alkenylene, R¹⁴ and R¹⁵ independentlyof one another represent hydrogen, represent in each case optionallysubstituted alkyl or alkenyl, R¹⁶ and R¹⁷ independently of one anotherrepresent hydrogen, represent optionally substituted alkyl orcycloalkyl, or R¹⁶ and R¹⁷ furthermore together represent optionallysubstituted alkylene, alkoxyalkylene or alkylthioalkylene, R¹⁸represents hydrogen, —SO₂R⁷, —COR⁷ or —CO₂R⁷; represents in each caseoptionally substituted alkyl, alkenyl, cycloalkyl, cycloalkylalkyl,aryl, arylalkyl or saturated or unsaturated heterocyclyl orheterocyclylalkyl, w represents 0, 1 or 2, n represents 1, 2, 3 or
 4. 2.The Δ¹ pyrroline of the Formula (I) according to claim 1, in which R¹represents halogen, alkyl, halogenoalkyl, alkoxy, halogenoalkoxy or—S(O)_(w)R⁴, R² and R³ independently of one another represent hydrogen,halogen, alkyl, halogenoalkyl, alkoxy, halogenoalkoxy or alkoxyalkyl, R⁴represents alkyl or halogenoalkyl, Het represents 5- to 14-memberedheteroaryl which comprises 1 to 3 aromatic rings and one or moreheteroatoms from the group consisting of nitrogen, oxygen and sulphurand is optionally mono- to tetrasubstituted by identical or differentR⁵, R⁵ represents the grouping —X—Y-Z-E, with the proviso that Y doesnot represent a direct bond if X does not represent a direct bond, Xrepresents a direct bond, oxygen, —S(O)_(w)—, —NR⁶—, carbonyl,carbonyloxy, oxycarbonyl, oxysulphonyl (OSO₂), alkylene,halogenoalkylene, alkenylene, halogenoalkenylene, alkinylene,alkyleneoxy, oxyalkylene, oxyalkyleneoxy, —S(O)_(w)-alkylene,cyclopropylene or oxiranylene, Y represents a direct bond or representsphenylene, naphthalene, tetrahydronaphthalene or 5- to 10-memberedsaturated or unsaturated heterocyclylene having one or more heteroatomsfrom the group consisting of nitrogen, oxygen and sulphur, each of whichradicals is optionally mono- to tetrasubstituted by identical ordifferent radicals from the list W¹, Z represents a direct bond or—(CH₂)_(n)—, E represents hydrogen, halogen, hydroxyl, cyano, formyl,nitro, trialkylsilyl, pentafluorothio, —S(O)_(w)R⁷, —OSO₂R⁷, —NR⁸R⁹,—COR⁷, —CO₂R⁷, —OC(O)R⁷, —CONR¹⁰R¹¹, —N(R¹²)COR¹³, —C(R¹⁴)═N—OR¹⁵,—SO₂NR¹⁶R¹⁷; represents alkyl, alkenyl, alkinyl, alkoxy, alkenyloxy;each of which is optionally mono- or polysubstituted by identical ordifferent substituents from the group consisting of halogen, cyano,alkoxy and/or —NR⁸R⁹; or represents cycloalkyl, cycloalkylalkyl,cycloalkyloxy, aryl, arylalkyl, aryloxy, aryloxyalkyl, saturated orunsaturated 5- to 10-membered heterocyclyl or heterocyclylalkyl havingone or more heteroatoms from the group consisting of nitrogen, oxygenand sulphur, each of which radicals is optionally mono- orpolysubstituted by identical or different substituents from the groupconsisting of halogen, cyano, nitro, alkyl, halogenoalkyl, alkenyl,halogenoalkenyl, alkoxy, halogenoalkoxy, alkylthio andhalogenoalkylthio, W¹ represents halogen, cyano, formyl, nitro,trialkylsilyl, alkyl, halogenoalkyl alkyl, alkoxy, halogenoalkoxy,alkenyl, halogenoalkenyl, alkenyloxy, halogenoalkenyloxy, alkylcarbonyl,alkoxycarbonyl, —S(O)_(w)R⁷, —C(R¹⁴)═N—OR¹⁵, —SO₂NR¹⁶R¹⁷,—(CH₂)_(p)NR¹⁶R¹⁷, —(CH₂)_(p)N(R¹⁶)COR¹⁷, —(CH₂)_(p)N(R¹⁶)SO₂R¹⁷,—OSO₂R¹⁶, —OSO₂NR¹⁶R¹⁷, R⁶ represents alkyl, halogenoalkyl or representscycloalkyl, cycloalkylalkyl, aryl or arylalkyl, each of which isoptionally mono- or polysubstituted by identical or differentsubstituents from the group consisting of halogen, alkyl, halogenoalkyl,alkoxy, halogenoalkoxy, alkylthio and/or halogenoalkylthio, R⁷represents alkyl which is optionally mono- or polysubstituted byidentical or different substituents from the group consisting of halogenand —NR⁸R⁹, represents cycloalkyl, aryl or arylalkyl, each of which isoptionally mono- or polysubstituted by identical or differentsubstituents from the group consisting of halogen, cyano, alkyl,halogenoalkyl, alkoxy, halogenoalkoxy, alkylthio and halogenoalkylthio,R⁸ and R⁹ independently of one another represent hydrogen, —SO₂R⁷,—COR⁷, —CO₂R⁷, represent alkyl or alkenyl, each of which is optionallymono- or polysubstituted by identical or different substituents from thegroup consisting of halogen, alkylcarbonyl, alkylcarbonyloxy,alkylamino, dialkylamino, alkoxy, halogenoalkoxy, alkylthio andhalogenoalkylthio; represents cycloalkyl, cycloalkylalkyl, aryl,arylalkyl or saturated or unsaturated 5- to 10-membered heterocyclyl orheterocyclylalkyl having one or more heteroatoms from the groupconsisting of nitrogen, oxygen and sulphur, each of which radicals isoptionally mono- or polysubstituted by identical or differentsubstituents from the group consisting of halogen, cyano, alkyl,halogenoalkyl, alkoxy, halogenoalkoxy, alkylthio and halogenoalkylthio,or R⁸ and R⁹ furthermore together represent alkenylene which isoptionally mono- or polysubstituted by identical or differentsubstituents from the group consisting of halogen, cyano, alkoxy,halogenoalkoxy, alkylthio and halogenoalkylthio or represent alkylenewhich is optionally mono- or polysubstituted by identical or differentsubstituents from the group consisting of halogen, cyano, alkyl,halogenoalkyl, alkoxy, halogenoalkoxy, alkylthio and halogenoalkylthio,where the alkylene chain may in each case be interrupted by —O—, —S— or—NR¹⁸—, R¹⁰ and R¹¹ independently of one another represent hydrogen,—SO₂R⁷, represent alkyl or alkenyl, each of which is optionally mono- orpolysubstituted by identical or different substituents from the groupconsisting of halogen, alkylamino, dialkylamino, alkoxy and alkylthio;represent cycloalkyl, cycloalkylalkyl, aryl, arylalkyl or saturated orunsaturated 5- to 10-membered heterocyclyl or heterocyclylalkyl havingone or more heteroatoms from the group consisting of nitrogen, oxygenand sulphur, each of which radicals is optionally mono- orpolysubstituted by identical or different substituents from the groupconsisting of halogen, cyano, alkyl, halogenoalkyl, alkoxy,halogenoalkoxy, alkylthio and halogenoalkylthio, or R¹⁰ and R¹¹furthermore together represent alkylene which is optionally mono- orpolysubstituted by identical or different substituents from the groupconsisting of halogen, cyano, alkyl, halogenoalkyl, alkoxy,halogenoalkoxy, alkylthio and halogenoalkylthio, where the alkylenechain may in each case be interrupted by —O—, —S— or —NR¹⁸—, R¹² and R¹³independently of one another represent hydrogen, represent alkyl whichis optionally mono- or polysubstituted by identical or differentsubstituents from the group consisting of cyano, alkoxy and alkylthio,represent cycloalkyl, cycloalkylalkyl, aryl or arylalkyl, each of whichis optionally mono- or polysubstituted by identical or differentsubstituents from the group consisting of halogen, cyano, alkyl,halogenoalkyl, alkoxy, halogenoalkoxy, alkylthio and halogenoalkylthio,or R¹² and R¹³ furthermore together represent alkylene or alkenylene,each of which is optionally mono- or polysubstituted by identical ordifferent substituents from the group consisting of halogen, alkyl,halogenoalkyl, alkoxy, halogenoalkoxy, alkylthio and halogenoalkylthio,R¹⁴ and R¹⁵ independently of one another represent hydrogen, representalkyl, halogenoalkyl, alkenyl or halogenoalkenyl, R¹⁶ and R¹⁷independently of one another represent hydrogen, alkyl, halogenoalkyl orrepresent cycloalkyl which is optionally mono- or polysubstituted byidentical or different substituents from the group consisting of halogenand alkyl, or R¹⁶ and R¹⁷ furthermore together represent alkylene,alkoxyalkylene or alkylthioalkylene, each of which is optionally mono-or polysubstituted by identical or different substituents from the groupconsisting of halogen and alkyl, R¹⁸ represents hydrogen, —SO₂R⁷, —COR⁷or —CO₂R⁷; represents alkyl or alkenyl, each of which is optionallymono- or polysubstituted by identical or different substituents from thegroup consisting of halogen, cyano, alkylamino, dialkylamino, alkoxy,halogenoalkoxy, alkylthio and halogenalkylthio; represents cycloalkyl,cycloalkylalkyl, aryl, arylalkyl, saturated or unsaturated 5- to10-membered heterocyclyl or heterocyclylalkyl having one or moreheteroatoms from the group consisting of nitrogen, oxygen and sulphur,each of which radicals is optionally mono- or polysubstituted byidentical or different substituents from the group consisting ofhalogen, cyano, alkyl, halogenoalkyl, alkoxy, halogenoalkoxy, alkylthioand halogenoalkylthio, w represents 0, 1 or 2, n represents 1, 2, 3 or4, p represents 0, 1 or
 2. 3. The Δ¹ pyrroline of the Formula (I)according to claim 1, in which R¹ represents halogen, C₁–C₆-alkyl,C₁–C₆-halogenoalkyl, C₁–C₆-alkoxy, C₁–C₆-halogenoalkoxy or —S(O)_(w)R⁴,R² and R³ independently of one another represent hydrogen, halogen,C₁–C₆-alkyl, C₁–C₆-halogenoalkyl, C₁–C₆-alkoxy, C₁–C₆-halogenoalkoxy orC₁–C₆-alkoxy-C₁–C₆-alkyl, R⁴ represents C₁–C₆-alkyl orC₁–C₆-halogenoalkyl, Het represents 5- to 14-membered heteroaryl whichcomprises 1 to 3 aromatic rings and 1 to 4 heteroatoms including 0 to 4nitrogen atoms, 0 to 2 nonadjacent oxygen atoms and/or 0 to 2nonadjacent sulphur atoms (in particular thienyl, benzothienyl, furyl,benzofuryl, indolyl, thienothienyl, thienofuryl, thienobenzothienyl,thienobenzofuryl, pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl,triazolyl or tetrazolyl), each of which radicals is optionally mono- totetrasubstituted by identical or different R⁵, R⁵ represents thegrouping —X—Y-Z-E, with the proviso that Y does not represent a directbond if X does not represent a direct bond, X represents a direct bond,oxygen, —S(O)_(w)—, —NR⁶—, carbonyl, carbonyloxy, oxycarbonyl,oxysulphonyl (OSO₂), C₁–C₆-alkylene, C₁–C₆-halogenoalkylene,C₂–C₆-alkenylene, C₂–C₆-halogenoalkenylene, C₂–C₆-alkinylene,C₁–C₆-alkyleneoxy, C₁–C₆-oxyalkylene, oxy-C₁–C₆-alkylene-oxy,—S(O)_(w)—C₁–C₆-alkylene, cyclopropylene or oxiranylene, Y represents adirect bond or represents 1,4-phenylene, 1,3-phenylene, 1,2-phenylene,2,6-naphthylene, 2,7-naphthylene, 1,4-naphthylene,2,6-(1,2,3,4-tetrahydro)naphthylene,2,7-(1,2,3,4-tetrahydro)-naphthylene,1,4-(1,2,3,4-tetrahydro)naphthylene,5,8-(1,2,3,4-tetrahydro)naphthylene, each of which is optionally mono-to tetrasubstituted by identical or different radicals from the list W¹;or represents 5- or 6-membered saturated or unsaturated heterocyclylenewhich comprises 1 to 3 heteroatoms including 0 to 3 nitrogen atoms, 0 to2 nonadjacent oxygen atoms and/or 0 to 2 nonadjacent sulphur atoms (inparticular furylene, thienylene, pyrrolylene, oxazolylene, thiazolylene,pyridinylene, pyrimidinylene, pyridazinylene or pyrazinylene), each ofwhich radicals is optionally mono- to tetrasubstituted by identical ordifferent radicals from the list W¹, Z represents a direct bond or—(CH₂)_(n)—, E represents hydrogen, fluorine, chlorine, bromine,hydroxyl, cyano, formyl, nitro, tri-(C₁–C₆-alkyl)silyl, pentafluorothio,—S(O)_(w)R⁷, —OSO₂R⁷, —NR⁸R⁹, —COR⁷, —CO₂R⁷, —OC(O)R⁷, —CONR¹⁰R¹¹,—N(R¹²)COR¹³, —C(R¹⁴)═N—OR¹⁵, —SO₂NR¹⁶R¹⁷; represents C₁–C₂₀-alkyl,C₂–C₂₀-alkenyl, C₂–C₁₀-alkinyl, C₁–C₂₀-alkoxy, C₂–C₂₀-alkenyloxy, eachof which is optionally mono- or polysubstituted by identical ordifferent radicals from the group consisting of halogen, cyano,C₁–C₁₀-alkoxy and —NR⁸R⁹; or represents C₃–C₁₂-cycloalkyl,C₃–C₇-cycloalkyl-C₁–C₄-alkyl, C₃–C₁₂-cycloalkyloxy, aryl,aryl-C₁–C₄-alkyl, aryloxy, aryloxy-C₁–C₄-alkyl, saturated or unsaturated5- to 10-membered heterocyclyl or heterocyclyl-C₁–C₄-alkyl whichcomprises 1 to 4 heteroatoms including 0 to 4 nitrogen atoms, 0 to 2nonadjacent oxygen atoms and/or 0 to 2 nonadjacent sulphur atoms (inparticular tetrazolyl, furyl, furfuryl, benzofuryl, tetrahydrofuryl,thienyl, thenyl, benzothienyl, thiolanyl, pyrrolyl, indolyl, pyrrolinyl,pyrrolidino, pyrrolidinyl, oxazolyl, benzoxazolyl, isoxazolyl,imidazolyl, pyrazolyl, thiazolyl, benzothiazolyl, thiazolidinyl,pyridinyl, pyrimidinyl, pyridazyl, pyrazinyl, piperidinyl, piperidino,morpholinyl, thiomorpholinyl, morpholino, thiomorpholino, triazinyl,triazolyl, quinolinyl or isoquinolinyl), each of which radicals isoptionally mono- to tetrasubstituted by identical or differentsubstituents from the group consisting of halogen, cyano, nitro,C₁–C₆-alkyl, C₁–C₆-halogenoalkyl, C₂–C₆-alkenyl, C₂–C₆ -halogenoalkenyl,C₁–C₆-alkoxy, C₁–C₆-halogenoalkoxy, C₁–C₆-alkylthio andC₁–C₆-halogenoalkylthio, W¹ represents fluorine, chlorine, bromine,cyano, formyl, nitro, tri-(C₁–C₆-alkyl)silyl, C₁–C₆-alkyl,C₁–C₆-halogenoalkyl, C₁–C₆-alkoxy, C₁–C₆-halo-genoalkoxy, C₂–C₆-alkenyl,C₂–C₆-halogenoalkenyl, C₂–C₆-alkenyloxy, C₂–C₆-halogenoalkenyloxy,C₁–C₆-alkylcarbonyl, C₁–C₆-alkoxycarbonyl, —S(O)_(w)R⁷, —C(R¹⁴)═N—OR¹⁵,—SO₂NR¹⁶R¹⁷, —(CH₂)_(p)NR¹⁶R¹⁷, —(CH₂)_(p)N(R¹⁶)COR¹⁷,—(CH₂)_(p)N(R¹⁶)SO₂R¹⁷, —OSO₂R¹⁶, —OSO₂NR¹⁶R¹⁷, R⁶ representsC₁–C₆-alkyl, C₁–C₆-halogenoalkyl or represents C₃–C₇-cycloalkyl,C₃–C₆-cycloalkyl-C₁–C₄-alkyl, aryl or aryl-C₁–C₄-alkyl, each of which isoptionally mono- to tetrasubstituted by halogen, C₁–C₆-alkyl,C₁–C₆-halogenoalkyl, C₁–C₆-alkoxy, C₁–C₆-halogenoalkoxy, C₁–C₆-alkylthioand C₁–C₆-halogenoalkylthio, R⁷ represents C¹C²⁰-alkyl which isoptionally mono- or polysubstituted by identical or differentsubstituents from the group consisting of halogen and —NR⁸R⁹, representsC₃–C₆-cycloalkyl, aryl or aryl-C₁–C₄-alkyl, each of which is optionallymono- to octasubstituted by identical or different substituents from thegroup consisting of halogen, cyano, C₁–C₆-alkyl, C₁–C₆-halogenoalkyl,C₁–C₆-alkoxy, C₁–C₆-halogenoalkoxy, C₁–C₆-alkylthio andC₁–C₆-halogenoalkylthio, R⁸ and R⁹ independently of one anotherrepresent hydrogen, —SO₂R⁷, —COR⁷, —CO₂R⁷, represent C₁–C₂₀-alkyl orC₂–C₂₀-alkenyl, each of which is optionally mono- or polysubstituted byidentical or different substituents from the group consisting ofhalogen, C₁–C₆-alkylcarbonyl, C₁–C₆-alkyl-carbonyloxy, C₁–C₆-alkylamino,di-(C₁–C₆-alkyl)amino, C₁–C₆-alkoxy, C₁–C₆-halogenoalkoxy,C₁–C₆-alkylthio, C₁–C₆-halogenoalkylthio; represent C₃–C₁₂-cycloalkyl,C₃–C₇-cycloalkyl-C₁–C₄-alkyl, aryl, aryl-C₁–C₄-alkyl or saturated orunsaturated 5- to 10-membered heterocyclyl or heterocyclyl-C₁–C₄-alkylwhich comprises 1 to 4 heteroatoms including 0 to 4 nitrogen atoms, 0 to2 nonadjacent oxygen atoms and/or 0 to 2 nonadjacent sulphur atoms (inparticular tetrazolyl, furyl, furfuryl, benzofuryl, tetrahydrofuryl,thienyl, thenyl, benzothienyl, thiolanyl, pyrrolyl, indolyl, pyrrolinyl,pyrrolidinyl, oxazolyl, benzoxazolyl, isoxazolyl, imidazolyl, pyrazolyl,thiazolyl, benzothiazolyl, thiazolidinyl, pyridinyl, pyrimidinyl,pyridazyl, pyrazinyl, piperidinyl, morpholinyl, thiomorpholinyl,triazinyl, triazolyl, quinolinyl or isoquinolinyl), each of whichradicals is optionally mono- to tetrasubstituted by identical ordifferent substituents from the group consisting of halogen, cyano,C₁–C₆-alkyl, C₁–C₆-halogenoalkyl, C₁–C₆-alkoxy, C₁–C₆-halogenoalkoxy,C₁–C₆-alkylthio or C₁–C₆-halogenoalkylthio, or R⁸ and R⁹ furthermoretogether represent C₂–C₁₂-alkenylene which is optionally mono- orpolysubstituted by identical or different substituents from the groupconsisting of halogen, cyano, C₁–C₆-alkoxy, C₁–C₆-halogenoalkoxy,C₁–C₆-alkylthio and C₁–C₆-halogenoalkylthio or represent C₃–C₁₂-alkylenewhich is optionally mono- or polysubstituted in the alkylene moiety byidentical or different substituents from the group consisting ofhalogen, cyano, C₁–C₆-alkyl, C₁–C₆-halogenoalkyl, C₁–C₆-alkoxy,C₁–C₆-halogenoalkoxy, C₁–C₆-alkylthio and C₁–C₆-halogenoalkylthio, wherethe alkylene chain may in each case be interrupted by —O—, —S— or—NR¹⁸—, R¹⁰ and R¹¹ independently of one another represent hydrogen,—SO₂R⁷, represents C₁–C₆-alkyl or C₂–C₆-alkenyl, each of which isoptionally mono- to tridecasubstituted by identical or differentsubstituents from the group consisting of halogen, C₁–C₆-alkylamino,di-(C₁–C₆-alkyl)amino, C₁–C₆-alkoxy, C₁–C₆-halogenoalkoxy,C₁–C₆-alkylthio and C₁–C₆ -halogenoalkylthio; representC₃–C₇-cycloalkyl, C₃–C₇-cycloalkyl-C₁–C₄-alkyl, aryl, aryl-C₁–C₄-alkylor saturated or unsaturated 5- to 10-membered heterocyclyl orheterocyclyl-C₁–C₄-alkyl which comprises 1 to 4 heteroatoms including 0to 4 nitrogen atoms, 0 to 2 nonadjacent oxygen atoms and/or 0 to 2nonadjacent sulphur atoms (in particular tetrazolyl, furyl, furfuryl,benzofuryl, tetrahydrofuryl, thienyl, thenyl, benzothienyl, thiolanyl,pyrrolyl, indolyl, pyrrolinyl, pyrrolidinyl, oxazolyl, benzoxazolyl,isoxazolyl, imidazolyl, pyrazolyl, thiazolyl, benzothiazolyl,thiazolidinyl, pyridinyl, pyrimidinyl, pyridazyl, pyrazinyl,piperidinyl, morpholinyl, thiomorpholinyl, triazinyl, triazolyl,quinolinyl or isoquinolinyl), each of which radicals is optionally mono-to tetrasubstituted by identical or different substituents from thegroup consisting of halogen, cyano, C₁–C₆-alkyl, C₁–C₆-halogenoalkyl,C₁–C₆-alkoxy, C₁–C₆-halogenoalkoxy, C₁–C₆-alkylthio andC₁–C₆-halogenoalkylthio, or R¹⁰ and R¹¹ furthermore together representC₃–C₆-alkylene, —(CH₂)₂—O—(CH₂)₂—, —(CH₂)₂—S—(CH₂)₂— or—(CH₂)₂—N(R¹⁸)—(CH₂)₂—, each of which is optionally mono- totetrasubstituted in the alkylene moiety by identical or differentsubstituents from the group consisting of halogen, cyano, C₁–C₆-alkyl,C₁–C₆-halogenoalkyl, C₁–C₆-alkoxy, C₁–C₆-halogenoalkoxy, C₁–C₆-alkylthioand C₁–C₆-halogenoalkylthio, R¹² and R¹³ independently of one anotherrepresent hydrogen, represent C₁–C₆-alkyl which is optionally mono- totridecasubstituted by identical or different substituents from the groupconsisting of halogen, cyano, C₁–C₆-alkoxy and C₁–C₆-alkylthio,represent C₃–C₇-cycloalkyl, C₃–C₇-cycloalkyl-C₁–C₄-alkyl, aryl oraryl-C₁–C₄-alkyl, each of which is optionally mono- to octasubstitutedby identical or different substituents from the group consisting ofhalogen, cyano, C₁–C₆-alkyl, C₁–C₆-halogenoalkyl, C₁–C₆-alkoxy,C₁–C₆-halogenoalkoxy, C₁–C₆-alkylthio and C₁–C₆-halogenoalkylthio, orR¹² and R¹³ furthermore together represent C₃–C₁₀-alkylene orC₃–C₁₀-alkenylene, each of which is optionally mono- to octasubstitutedby identical or different substituents from the group consisting ofhalogen, C₁–C₆-alkyl, C₁–C₆-halogenoalkyl, C₁–C₆-alkoxy,C₁–C₆-halogenoalkoxy, C₁–C₆-alkylthio and C₁–C₆-halogenoalkylthio, R¹⁴and R¹⁵ independently of one another represent hydrogen, representC₁–C₆-alkyl, C₁–C₆-halogenoalkyl, C₂–C₆-alkenyl orC₂–C₆-halogenoalkenyl, R¹⁶ and R¹⁷ independently of one anotherrepresent hydrogen, C₁–C₆-alkyl, C₁–C₆-halogenoalkyl or representC₃–C₇-cycloalkyl which is optionally mono- to octasubstituted byidentical or different substituents from the group consisting offluorine, chlorine, bromine and/or C₁–C₆-alkyl, or R¹⁶ and R¹⁷furthermore together represent C₃–C₆-alkylene,C₁–C₃-alkoxy-C₁–C₃-alkylene or C₁–C₃-alkylthio-C₁–C₃-alkylene, each ofwhich is optionally mono- to nonasubstituted by identical or differentsubstituents from the group consisting of fluorine, chlorine, bromineand C₁–C₆-alkyl, R¹⁸ represents hydrogen, —SO₂R⁷, —COR⁷ or —CO₂R⁷;represents C₁–C₂₀-alkyl or C₂–C₂₀-alkenyl, each of which is optionallymono- or polysubstituted by identical or different substituents from thegroup consisting of halogen, cyano, C₁–C₆-alkylamino,di-(C₁–C₆-alkyl)amino, C₁–C₆-alkoxy, C₁–C₆-halogenoalkoxy,C₁–C₆-alkylthio and C₁–C₆-halogenoalkylthio; representsC₃–C₁₂-cycloalkyl, C₃–C₇-cycloalkyl-C₁–C₄-alkyl, aryl, aryl-C₁–C₄-alkyl,saturated or unsaturated 5- to 10-membered heterocyclyl orheterocyclyl-C₁–C₄-alkyl which comprises 1 to 4 heteroatoms including 0to 4 nitrogen atoms, 0 to 2 nonadjacent oxygen atoms and/or 0 to 2nonadjacent sulphur atoms (in particular tetrazolyl, furyl, furfuryl,benzofuryl, tetrahydrofuryl, thienyl, thenyl, benzothienyl, thiolanyl,pyrrolyl, indolyl, pyrrolinyl, pyrrolidinyl, oxazolyl, benzoxazolyl,isoxazolyl, imidazolyl, pyrazolyl, thiazolyl, benzothiazolyl,thiazolidinyl, pyridinyl, pyrimidinyl, pyridazyl, pyrazinyl,piperidinyl, morpholinyl, thiomorpholinyl, triazinyl, triazolyl,quinolinyl or isoquinolinyl), each of which radicals is optionally mono-to tetrasubstituted by identical or different substituents from thegroup consisting of halogen, cyano, C₁–C₆-alkyl, C₁–C₆-halogenoalkyl,C₁–C₆-alkoxy, C₁–C₆-halogenoalkoxy, C₁–C₆-alkylthio andC₁–C₆-halogenoalkylthio, w represents 0, 1 or 2, n represents 1, 2 or 3,p represents 0, 1 or
 2. 4. The Δ¹ pyrroline of the Formula (I) accordingto claim 1, in which R¹ represents fluorine, chlorine, bromine,C₁–C₄-alkyl, C₁–C₄-halogenoalkyl having 1 to 9 fluorine, chlorine and/orbromine atoms, C₁–C₄-alkoxy, C₁–C₄-halogenoalkoxy having 1 to 9fluorine, chlorine and/or bromine atoms or —S(O)_(w)R⁴, R² and R³independently of one another represent hydrogen, fluorine, chlorine,bromine, C₁–C₄-alkyl, C₁–C₄-halogenoalkyl having 1 to 9 fluorine,chlorine and/or bromine atoms, C₁–C₄-alkoxy or C₁–C₄-halogenoalkoxyhaving 1 to 9 fluorine, chlorine and/or bromine atoms, R⁴ representsC₁–C₄-alkyl or represents in each case fluorine- or chlorine-substitutedmethyl or ethyl, Het represents 2-thienyl, 3-thienyl, 2-benzo[b]thienyl,2-furyl, 3-furyl, 2-benzo[b]furyl, 2-indolyl, 2-thieno[3,2-b]thienyl,2-thieno[3,2-b]furyl, 5-thieno[3,2-b]furyl,2-thieno[2,3-f][1]benzothienyl, 2-thieno[2,3-f][1]benzo-furyl,6-thieno[2,3-f]]1]benzofuryl, 2-pyridinyl, 3-pyridinyl, 2-pyrimidinyl,5-pyrimidinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrazinyl, triazolyl ortetrazolyl, each of which is optionally mono- to trisubstituted byidentical or different R⁵, R⁵ represents the grouping —X—Y-Z-E, with theproviso that Y does not represent a direct bond if X does not representa direct bond, X represents a direct bond, oxygen —S(O)_(w)—, —NR⁶—,carbonyl, carbonyloxy, oxycarbonyl, oxysulphonyl (OSO₂), C₁–C₄-alkylene,C₁–C₄-halogenoalkylene having 1 to 8 fluorine, chlorine and/or bromineatoms, C₂–C₄-alkenylene, C₂–C₄-halogenoalkenylene having 1 to 6fluorine, chlorine and/or bromine atoms, C₂–C₄-alkinylene,C₁–C₄-alkyleneoxy, oxy-C₁–C₄-alkylene, oxy-C₁–C₄-alkyleneoxy or—S(O)_(w)—C₁–C₄-alkylene, Y represents a direct bond or represents1,4-phenylene, 1,3-phenylene, 1,2-phenylene, 2,6-naphthylene,2,7-naphthylene, 1,4-naphthylene, 2,6-(1,2,3,4-tetrahydro)naphthylene,2,7-(1,2,3,4-tetrahydro)-naphthylene,1,4-(1,2,3,4-tetrahydro)naphthylene,5,8-(1,2,3,4-tetrahydro)naphthylene, 2,4-furylene, 2,4-thienylene,2,4-pyrrolylene, 2,5-oxazolylene, 2,5-thiazolylene, 2,5-pyridinylene,2,6-pyridinylene, 2,5-pyrimidinylene, 3,6-pyridazinylene or2,5-pyrazinylene, each of which is optionally mono- to trisubstituted byidentical or different radicals from the list W¹, Z represents a directbond or —(CH₂)_(n)—, E represents hydrogen, fluorine, chlorine, bromine,hydroxyl, cyano, formyl, nitro, trimethylsilyl,dimethyl-tert-butylsilyl, —S(O)_(w)R⁷, —OSO₂R⁷, —NR⁸R⁹, —COR⁷, —CO₂R⁷,—OC(O)R⁷, —CONR¹⁰R¹¹, —N(R¹²)COR¹³, —SO₂NR¹⁶R¹⁷; representsC₁–C₁₆-alkyl, C₂–C₁₆-alkenyl, C₂–C₆-alkinyl, C₁–C₁₆-alkoxy,C₂–C₁₆-alkenyloxy, each of which is optionally mono- or polysubstitutedby identical or different substituents from the group consisting offluorine, chlorine, bromine, cyano, C₁–C₆-alkoxy and —NR⁸R⁹; orrepresents C₃–C₁₀-cycloalkyl, C₃–C₆-cycloalkyl-C₁–C₄-alkyl,C₃–C₁₀-cycloalkyloxy, phenyl, phenoxy, benzyl, phenylethyl, benzyloxy,tetrazolyl, furyl, furfuryl, benzofuryl, tetrahydrofuryl, thienyl,thenyl, benzothienyl, thiolanyl, pyrrolyl, indolyl, pyrrolinyl,pyrrolidino, pyrrolidinyl, oxazolyl, benzoxazolyl, isoxazolyl,imidazolyl, pyrazolyl, thiazolyl, benzothiazolyl, thiazolidinyl,pyridinyl, pyrimidinyl, pyridazyl, pyrazinyl, piperidinyl, piperidino,morpholinyl, thiomorpholinyl, morpholino, thiomorpholino, triazinyl,triazolyl, quinolinyl or isoquinolinyl, each of which is optionallymono- to trisubstituted by identical or different substituents from thegroup consisting of fluorine, chlorine, bromine, cyano, C₁–C₄-alkyl,C₁–C₄-halogenoalkyl, C₂–C₆-alkenyl, C₂–C₆-halogenoalkenyl, C₁–C₄-alkoxy,C₁–C₄-halogenoalkoxy, C₁–C₄-alkylthio and C₁–C₄-halogenoalkylthio, W¹represents fluorine, chlorine, bromine, cyano, formyl, trimethylsilyl,dimethyl-tert-butylsilyl, C₁–C₄-alkyl, C₁–C₄-alkoxy, C₂–C₄-alkenyl,C₂–C₄-alkenyloxy; represents C₁–C₄-halogenoalkyl, C₁–C₄-halogenoalkoxyhaving in each case 1 to 9 fluorine, chlorine and/or bromine atoms,C₂–C₄-halogenoalkenyl, C₂–C₄-halogenoalkenyloxy having in each case 1 to8 fluorine, chlorine and/or bromine atoms; representsC₁–C₄-alkylcarbonyl, C₁–C₄-alkoxycarbonyl, —S(O)_(w)R⁷, —SO₂NR¹⁶R¹⁷,—(CH₂)_(p)NR¹⁶R¹⁷, —(CH₂)_(p)N(R¹⁶)COR¹⁷, —(CH₂)_(p)N(R¹⁶)SO₂R¹⁷,—OSO₂R¹⁶, —OSO₂NR¹⁶R¹⁷, R⁶ represents methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, trifluoromethyl,trifluoroethyl, or represents cyclopropyl, cyclopropylmethyl,cyclopentyl, cyclopentylmethyl, cyclohexyl, cyclohexylmethyl, phenyl,benzyl or phenylethyl, each of which is optionally mono- totetrasubstituted by identical or different substituents from the groupconsisting of fluorine, chlorine, bromine, C₁–C₄-alkyl, C₁–C₄-alkoxy,C₁–C₄-alkylthio, C₁–C₄-halogenoalkyl, C₁–C₄-halogenoalkoxy andC₁–C₄-halogenoalkylthio having in each case 1 to 9 fluorine, chlorineand/or bromine atoms, R⁷ represents C₁–C₁₀-alkyl which is optionallymono- or polysubstituted by identical or different substituents from thegroup consisting of fluorine, chlorine, bromine and —NR⁸R⁹, representscyclopropyl, cyclopentyl, cyclohexyl, phenyl or benzyl, each of which isoptionally mono- to tetrasubstituted by identical or differentsubstituents from the group consisting of fluorine, chlorine, bromine,cyano, C₁–C₄-alkyl, C₁–C₄-alkoxy, C₁–C₄-alkylthio, C₁–C₄-halogenoalkyl,C₁–C₄-halogenoalkoxy and C₁–₄-halogenoalkylthio, R⁸ and R⁹ independentlyof one another represent hydrogen, —SO₂R⁷, —COR⁷, —CO₂R⁷, representC₁–C₁₆-alkyl or C₂–C₁₆-alkenyl, each of which is optionally mono- orpolysubstituted by identical or different substituents from the groupconsisting of fluorine, chlorine, bromine, C₁–C₄-alkyl-carbonyl,C₁–C₄-alkylcarbonyloxy, C₁–C₄-alkylamino, di-(C₁–C₄-alkyl)-amino,C₁–C₄-alkoxy, C₁–C₄-halogenoalkoxy, C₁–C₄-alkylthio andC₁–C₄-halogenoalkylthio; represent C₃–C₁₀-cycloalkyl,C₃–C₆-cycloalkyl-C₁–C₄-alkyl, phenyl, benzyl, phenylethyl, tetrazolyl,furyl, furfuryl, benzofuryl, tetrahydrofuryl, thienyl, thenyl,benzothienyl, thiolanyl, pyrrolyl, indolyl, pyrrolinyl, pyrrolidinyl,oxazolyl, benzoxazolyl, isoxazolyl, imidazolyl, pyrazolyl, thiazolyl,benzothiazolyl, thiazolidinyl, pyridinyl, pyrimidinyl, pyridazyl,pyrazinyl, piperidinyl, morpholinyl, thiomorpholinyl, triazinyl,triazolyl, quinolinyl or isoquinolinyl, each of which is optionallymono- to trisubstituted by identical or different substituents from thegroup consisting of fluorine, chlorine, bromine, cyano, C₁–C₄-alkyl,C₁–C₄-halogenoalkyl, C₁–C₄-alkoxy, C₁–C₄-halogenoalkoxy, C₁–C₄-alkylthioand C₁–C₄-halogenoalkylthio, or R⁸ and R⁹ furthermore together representC₂C₁₀-alkenylene which is optionally mono- or polysubstituted byidentical or different substituents from the group consisting offluorine, chlorine, bromine, C₁–C₄-alkoxy, C₁–C₄-halogenoalkoxy,C₁–C₄-alkylthio and C₁–C₄-halogenoalkylthio or representC₃–C₁₀-alkylene, which is optionally mono- or polysubstituted in thealkylene moiety by identical or different substituents from the groupconsisting of fluorine, chlorine, cyano, C₁–C₄-alkyl,C₁–C₄-halogenoalkyl, C₁–C₄-alkoxy, C₁–C₄-halogenoalkoxy, C₁–C₄-alkylthioand C₁–C₄-halogenoalkylthio, where the alkylene chain may in each casebe interrupted by —O—, —S— or —NR¹⁸—, R¹⁰ and R¹¹ independently of oneanother represent hydrogen, —SO₂R⁷, represent C₁–C₆-alkyl orC₂–C₆-alkenyl, each of which is optionally mono- to nonasubstituted byidentical or different substituents from the group consisting offluorine, chlorine, bromine, C₁–C₄-alkylamino, di-(C₁–C₄-alkyl)amino,C₁–C₄-alkoxy, C₁–C₄-halogenoalkoxy, C₁–C₄-alkylthio andC₁–C₄-halogenoalkylthio; represent C₃–C₆-cycloalkyl,C₃–C₆-cycloalkyl-C₁–C₄-alkyl, phenyl, benzyl, phenylethyl, tetrazolyl,furyl, furfuryl, benzofuryl, tetrahydrofuryl, thienyl, thenyl,benzothienyl, thiolanyl, pyrrolyl, indolyl, pyrrolinyl, pyrrolidinyl,oxazolyl, benzoxazolyl, isoxazolyl, imidazolyl, pyrazolyl, thiazolyl,benzothiazolyl, thiazolidinyl, pyridinyl, pyrimidinyl, pyridazyl,pyrazinyl, piperidinyl, morpholinyl, thiomorpholinyl, triazinyl,triazolyl, quinolinyl or isoquinolinyl, each of which is optionallymono- to trisubstituted by identical or different substituents from thegroup consisting of fluorine, chlorine, bromine, cyano, C₁–C₄-alkyl,C₁–C₄-halogenoalkyl, C₁–C₄-alkoxy, C₁–C₄-halogenoalkoxy, C₁–C₄-alkylthioand C₁–C₄-halogenoalkylthio, or R¹⁰ and R¹¹ furthermore togetherrepresent C₄–C₆-alkylene, —(CH₂)₂—O—(CH₂)₂—, —(CH₂)₂—S—(CH₂)₂— or—(CH₂)₂—N(R¹⁸)—(CH₂)₂—, each of which is optionally mono- totetrasubstituted in the alkylene moiety by identical or differentsubstituents from the group consisting of fluorine, chlorine, cyano,C₁–C₄-alkyl, C₁–C₄-halogenoalkyl, C₁–C₄-alkoxy, C₁–C₄-halogenoalkoxy,C₁–C₄-alkylthio and C₁–C₄-halogenoalkylthio, R¹² and R¹³ independentlyof one another represent hydrogen, represent C₁–C₆-alkyl which isoptionally mono- to nonasubstituted by identical or differentsubstituents from the group consisting of fluorine, chlorine, bromine,C₁–C₄-alkoxy and C₁–C₄-alkylthio, represent C₃–C₆-cycloalkyl,C₃–C₆-cycloalkyl-C₁–C₄-alkyl, phenyl, benzyl or phenylethyl, each ofwhich is optionally mono- to tetrasubstituted by identical or differentsubstituents from the group consisting of fluorine, chlorine, bromine,C₁–C₄-alkyl, C₁–C₄-halogenoalkyl, C₁–C₄-alkoxy, C₁–C₄-halogenoalkoxy,C₁–C₄-alkylthio and C₁–C₄-halogenoalkylthio, or R¹² and R¹³ furthermoretogether represent C₃–C₈-alkylene or C₃–C₈-alkenylene, each of which isoptionally mono- to tetrasubstituted by identical or differentsubstituents from the group consisting of fluorine, chlorine, bromine,C₁–C₄-alkyl, C₁–C₄-halogenoalkyl, C₁–C₄-alkoxy, C₁–C₄-halogenoalkoxy,C₁–C₄-alkylthio and C₁–C₄-halogenoalkylthio, R¹⁶ and R¹⁷ independentlyof one another represent hydrogen, C₁–C₆-alkyl, C₁–C₄-halogenoalkylhaving 1 to 9 fluorine, chlorine and/or bromine atoms or representC₃–C₆-cycloalkyl which is optionally mono- to tetrasubstituted byidentical or different substituents from the group consisting offluorine, chlorine, bromine and C₁–C₄-alkyl, or R¹⁶ and R¹⁷ furthermoretogether represent —(CH₂)₃—, —(CH₂)₄—, —(CH₂)₅—, —(CH₂)₂—O—(CH₂)₂— or—(CH₂)₂—S—(CH₂)₂—, R¹⁸ represents hydrogen, —SO₂R⁷, represents —COR⁷ or—CO₂R⁷; represents C₁–C₁₆-alkyl or C₂–C₁₆-alkenyl, each of which isoptionally mono- or polysubstituted by identical or differentsubstituents from the group consisting of fluorine, chlorine, bromine,cyano, methylamino, ethylamino, di-(C₁–C₆-alkyl)amino, C₁–C₄-alkoxy,C₁–C₄-halogenoalkoxy, C₁–C₄-alkylthio and C₁–C₄-halogenoalkylthio;represents C₃–C₁₀-cycloalkyl, C₃–C₆-cycloalkyl-C₁–C₄-alkyl, phenyl,benzyl, phenylethyl, tetrazolyl, furyl, furfuryl, benzofuryl,tetrahydrofuryl, thienyl, thenyl, benzothienyl, thiolanyl, pyrrolyl,indolyl, pyrrolinyl, pyrrolidinyl, oxazolyl, benzoxazolyl, isoxazolyl,imidazolyl, pyrazolyl, thiazolyl, benzothiazolyl, thiazolidinyl,pyridinyl, pyrimidinyl, pyridazyl, pyrazinyl, piperidinyl, morpholinyl,thiomorpholinyl, triazinyl, triazolyl, quinolinyl or isoquinolinyl, eachof which is optionally mono- to trisubstituted by identical or differentsubstituents from the group consisting of fluorine, chlorine, bromine,cyano, C₁–C₄-alkyl, C₁–C₄-halogenoalkyl, C₁–C₄-alkoxy,C₁–C₄-halogenoalkoxy, C₁–C₄-alkylthio and C₁–C₄-halogenoalkylthio, wrepresents 0, 1 or 2, n represents 1 or 2, p represents 0 or
 1. 5. TheΔ¹ pyrroline of the Formula (I) according to claim 1, in which R¹represents fluorine, chlorine, bromine, methyl, trifluoromethyl,methoxy, trifluoromethoxy, methylthio or trifluoromethylthio, R² and R³independently of one another represent hydrogen, fluorine, chlorine,bromine, methyl, trifluoromethyl, methoxy or trifluoromethoxy, Hetrepresents 2-thienyl, 3-thienyl, 2-benzo[b]thienyl, 2-furyl, 3-furyl,2-benzo[b]furyl, 2-thieno[3,2-b]thienyl, 2-thieno[3,2-b]furyl,5-thieno[3,2-b]furyl, 2-thieno[2,3-f][1]benzothienyl,2-thieno[2,3-f][1]benzofuryl, 6-thieno[2,3-f][1]benzofuryl, 2-pyridinyl,3-pyridinyl, 2-pyrimidinyl, 5-pyrimidinyl, 3-pyridazinyl, 4-pyridazinylor 2-pyrazinyl, each of which is optionally mono- or disubstituted byidentical or different R⁵, R⁵ represents the grouping —X—Y-Z-E, with theproviso that Y does not represent a direct bond if X does not representa direct bond, X represents a direct bond, oxygen, sulphur, —SO₂—,—NR⁶—, —CO—, —C(O)—O—, —O—C(O)—, —CH₂—, —(CH₂)₂—, —C═C— (E or Z), —C≡C—,—CH₂—O—, —(CH₂)₂O—, —OCH₂—, —O(CH₂)₂—, —O—CH₂—O—, —SCH₂—, —S(CH₂)₂—,—CH₂S— or —(CH₂)₂S—, Y represents a direct bond or represents1,4-phenylene, 1,3-phenylene, 2,6-naphthylene, 2,7-naphthylene,2,4-furylene, 2,4-thienylene, 2,5-pyridinylene, 2,5-pyrimidinylene,3,6-pyridazinylene or 2,5-pyrazinylene, each of which is optionallymono- or disubstituted by identical or different dicals from the listW¹, Z represents a direct bond, methylene or ethylene, E representshydrogen, fluorine, chlorine, bromine, hydroxyl, cyano, formyl,—S(O)_(w)R⁷, —OSO₂R⁷, —NR⁸R⁹, —COR⁷, —CO₂R⁷, —OC(O)R⁷, —CONR¹⁰R¹¹,—N(R¹²)COR¹³, —SO₂NR¹⁶R¹⁷; represents C₁–C₁₆-alkyl, C₂–C₁₆-alkenyl,C₁–C₁₆-alkoxy, C₂–C₁₆-alkenyloxy, each of which is optionally mono- orpolysubstituted by identical or different substituents from the groupconsisting of fluorine, chlorine, bromine, cyano, C₁–C₆-alkoxy and—NR⁸R⁹; or represents cyclopropyl, cyclopentyl, cyclohexyl,cyclopropyloxy, cyclopentyloxy, cyclohexyloxy, cyclopropylmethyl,cyclopentylmethyl, cyclohexylmethyl, phenyl, phenoxy, benzyl,phenylethyl, benzyloxy, tetrazolyl, furyl, furfuryl, benzofuryl,tetrahydrofuryl, thienyl, thenyl, benzothienyl, thiolanyl, pyrrolyl,indolyl, pyrrolinyl, pyrrolidino, pyrrolidinyl, oxazolyl, benzoxazolyl,isoxazolyl, imidazolyl, pyrazolyl, thiazolyl, benzothiazolyl,thiazolidinyl, pyridinyl, pyrimidinyl, pyridazyl, pyrazinyl,piperidinyl, piperidino, morpholinyl, thiomorpholinyl, morpholino,thiomorpholino, triazinyl, triazolyl, quinolinyl or isoquinolinyl, eachof which is optionally mono- to trisubstituted by identical or differentsubstituents from the group consisting of fluorine, chlorine, bromine,cyano, methyl, ethyl, n-propyl, isopropyl, —CF₃, —CHF₂, —CClF₂,—CF₂CHFCl, —CF₂CH₂F, —CF₂CCl₃, —CH₂CF₃, —CF₂CHFCF₃, —CH₂CF₂H,—CH₂CF₂CF₃, —CF₂CF₂H, —CF₂CHFCF₃, vinyl, allyl, 1-propenyl, butenyl,—CF═CHF, —CF═CH₂, —CF═CCl₂, —CH═CF₂, —CF₂CF═CF₂, —CH═CFH, —CH₂CF═CF₂,—CF═CF₂, —CF₂CH═CF₂, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy,isobutoxy, sec-butoxy, tert-butoxy, trifluoromethoxy, difluoromethoxy,chlorodifluoromethoxy, trifluoroethoxy, methylthio, ethylthio,n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio,tert-butylthio, trifluoromethylthio, difluoromethylthio,chlorodifluoromethylthio and trifluoroethylthio, W¹ represents fluorine,chlorine, bromine, cyano, formyl, methyl, ethyl, n-propyl, isopropyl,n-butyl, isobutyl, sec-butyl, tert-butyl, methoxy, ethoxy, n-propoxy,isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, vinyl, allyl,trifluoromethyl, trifluoroethyl, trifluoromethoxy, trifluoroethoxy,—OCF₂CF₂H, —CH═CF₂, —CH═CCl₂, —OCF═CF₂, —COMe, —COEt, —CO₂Me, —CO₂Et,—CO₂(t-Bu), —SMe, —SOMe, —SO₂Me, —SCF₃, —SOCF₃, —SO₂CF₃, —SCHF₂,—SOCHF₂, —SO₂CHF₂, —SO₂NMe₂, —NMe₂, —NEt₂, —N(n-Pr)₂, —N(Me)COMe,—N(Me)COEt, —N(Me)COPr, —N(Me)CO(t-Bu), 2-pyrrolidonyl, 2-piperidonyl,—N(Me)SO₂Me, —N(Me)SO₂Et, —N(Me)SO₂CF₃, —N(Et)SO₂CF₃, —N(Me)SO₂(CF₂)₃CF₃or —OSO₂NMe₂, R⁶ represents methyl, ethyl, n-propyl, isopropyl, n-butyl,isobutyl, sec-butyl, tert-butyl, trifluoromethyl, trifluoroethyl,cyclopropyl, cyclopropylmethyl, cyclopentyl, cyclopentylmethyl,cyclohexyl, cyclohexylmethyl, phenyl, benzyl or phenylethyl, R⁷represents methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,sec-butyl, tert-butyl, pentyl, hexyl, —CF₃, —CHF₂, —CCl₃, —CCl₂F,dimethyl aminomethyl, dimethylaminoethyl, diethylaminomethyl,diethylaminoethyl, cyclopropyl, cyclopentyl, cyclohexyl, phenyl orbenzyl, R⁸ and R⁹ independently of one another represent hydrogen,—SO₂R⁷, —COR⁷, —CO₂R⁷, represent C₁–C₁₆-alkyl or C₂≠C₄-alkenyl, each ofwhich is optionally mono- or polysubstituted by identical or differentsubstituents from the group consisting of fluorine, chlorine, bromine,C₁–C₄-alkylcarbonyl, C₁–C₄-alkylcarbonyloxy, C₁–C₄-alkylamino,di-(C₁–C₄-alkyl)amino, C₁–C₄-alkoxy, C₁–C₄-halogenoalkoxy,C₁–C₄-alkylthio and C₁–C₄-halogenoalkylthio; represent C₃–C₈-cycloalkyl,cyclopropylmethyl, cyclopentylmethyl, cyclohexylmethyl,cyclopropylethyl, cyclopentylethyl, cyclohexylethyl, phenyl, benzyl,phenylethyl, tetrazolyl, furyl, furfuryl, benzofuryl, tetrahydrofuryl,thienyl, thenyl, benzothienyl, thiolanyl, pyrrolyl, indolyl, pyrrolinyl,pyrrolidinyl, oxazolyl, benzoxazolyl, isoxazolyl, imidazolyl, pyrazolyl,thiazolyl, benzothiazolyl, thiazolidinyl, pyridinyl, pyrimidinyl,pyridazyl, pyrazinyl, piperidinyl, morpholinyl, thiomorpholinyl,triazinyl, triazolyl, quinolinyl or isoquinolinyl, each of which isoptionally mono- to trisubstituted by identical or differentsubstituents from the group consisting of fluorine, chlorine, bromine,cyano, C₁–C₄-alkyl, C₁–C₄-halogenoalkyl, C₁–C₄-alkoxy,C₁–C₄-halogenoalkoxy, C₁–C₄-alkylthio and C₁–C₄-halogenoalkylthio, or R⁸and R⁹ furthermore together represent C₂–C₈-alkenylene which isoptionally mono- or polysubstituted by identical or differentsubstituents from the group consisting of fluorine, chlorine, bromine,C₁–C₄-alkoxy, C₁–C₄-halogenoalkoxy, C₁–C₄-alkylthio andC₁–C₄-halogenoalkylthio or represent C₃–C₈-alkylene, which is optionallymono- or polysubstituted in the alkylene moiety by identical ordifferent substituents from the group consisting of fluorine, chlorine,cyano, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl,tert-butyl, C₁–C₄-halogenoalkyl, methoxy, ethoxy, n-propoxy, isopropoxy,n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, C₁–C₄-halogenoalkoxy,methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio,isobutylthio, sec-butylthio, tert-butylthio and C₁–C₄-halogenoalkylthio,where the alkylene chain may in each case be interrupted by —O—, —S— or—NR¹⁸—, R¹⁰ and R¹¹ independently of one another represent hydrogen,—SO_(2CF) ₃, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,sec-butyl, tert-butyl, pentyl, hexyl, —CF₃, —CH₂CF₃, —(CF₂)₃CF₃,methoxymethyl, methoxyethyl, cyclopropyl, cyclopentyl, cyclohexyl, orrepresent phenyl or benzyl, each of which is optionally mono- totrisubstituted by identical or different substituents from the groupconsisting of fluorine, chlorine, bromine, methyl, trifluoromethyl,methoxy and trifluoromethoxy, or R¹⁰ and R¹¹ furthermore togetherrepresent —(CH₂)₄—, —(CH₂)₅—, —(CH₂)₆—, —CH₂—CH(CH₃)—CH₂—CH(CH₃)—CH₂—,—(CH₂)₂—O—(CH₂)₂—, —(CH₂)₂—S—(CH₂)₂— or —(CH₂)₂—N(R¹⁸)—(CH₂)₂—, R¹² andR¹³ independently of one another represent hydrogen, methyl, ethyl,n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-hexyl,trifluoromethyl, trifluoroethyl, cyclopropyl, cyclopentyl, cyclohexyl orrepresent phenyl or benzyl, each of which is optionally mono- totetrasubstituted by identical or different substituents from the groupconsisting of fluorine, chlorine, bromine, methyl, trifluoromethyl,methoxy and trifluoromethoxy, or R¹² and R¹³ furthermore togetherrepresent —(CH₂)₃—, —(CH₂)₄—, —(CH₂)₅— or —(CH₂)₆—, each of which isoptionally mono- to tetrasubstituted by identical or differentsubstituents from the group consisting of fluorine, chlorine, bromine,methyl, ethyl, methoxy, ethoxy, methylthio, ethylthio, trifluoromethyl,trifluoromethoxy and trifluoromethylthio, R¹⁶ and R¹⁷ independently ofone another represent hydrogen, methyl, ethyl, n-propyl, isopropyl,n-butyl, isobutyl, sec-butyl, tert-butyl, n-hexyl, trifluoromethyl,trifluoroethyl, cyclopropyl, cyclopentyl or cyclohexyl, or R¹⁶ and R¹⁷furthermore together represent —(CH₂)₃—, —(CH₂)₄—, —(CH₂)₅—,—(CH₂)₂—O—(CH₂)₂— or —(CH₂)₂—S—(CH₂)₂, R¹⁸ represents hydrogen, —SO₂R⁷,represents —COR⁷ or —CO₂R⁷; represents C₁–C₁₆-alkyl or C₂–C₁₆-alkenyl,each of which is optionally mono- or polysubstituted by identical ordifferent substituents from the group consisting of fluorine, chlorine,bromine, cyano, methylamino, ethylamino, di-(C₁–C₄-alkyl)amino,C₁–C₄-alkoxy, C₁–C₄-halogenoalkoxy, C₁–C₄-alkylthio andC₁–C₄-halogenoalkylthio; represents C₃–C₈-cycloalkyl, cyclopropylmethyl,cyclopentylmethyl, cyclohexylmethyl, cyclopropylethyl, cyclopentylethyl,cyclohexylethyl, phenyl, benzyl, phenylethyl, tetrazolyl, furyl,furfuryl, benzofuryl, tetrahydrofuryl, thienyl, thenyl, benzothienyl,thiolanyl, pyrrolyl, indolyl, pyrrolinyl, pyrrolidinyl, oxazolyl,benzoxazolyl, isoxazolyl, imidazolyl, pyrazolyl, thiazolyl,benzothiazolyl, thiazolidinyl, pyridinyl, pyrimidinyl, pyridazyl,pyrazinyl, piperidinyl, morpholinyl, thiomorpholinyl, triazinyl,triazolyl, quinolinyl or isoquinolinyl, each of which is optionallymono- to trisubstituted by identical or different substituents from thegroup consisting of fluorine, chlorine, bromine, cyano, methyl, ethyl,n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl,C₁–C₄-halogenoalkyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy,isobutoxy, sec-butoxy, tert-butoxy, C₁–C₄-halogenoalkoxy, methylthio,ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutyithio,sec-butylthio, tert-butylthio and C₁–C₄-halogenoalkylthio.
 6. A Δ¹pyrroline of the Formula

in which R¹ represents fluorine or chlorine, R² represents hydrogen orfluorine and Het has the meaning given in claim
 1. 7. A compound of theFormulae (I-1) to (I-16)

in which in each case R¹ represents fluorine or chlorine, R² representshydrogen or fluorine and R⁵ has the meaning given in claim
 1. 8. Acompound of the Formula (I-d) having the (R)-configuration

in which R¹, R², R³ and Het have the meanings given in claim
 1. 9. TheΔ¹ pyrroline of the Formula (I) according to claim 1 in which Hetrepresents 2-thienyl, 3-thienyl, 2-thieno[3,2-b]-thienyl, 2-pyridinyl or3-pyridinyl, each of which is optionally mono- or disubstituted byidentical or different R⁵ .
 10. The Δ¹ pyrroline of the Formula (I)according to claim 1 in which R¹ represents fluorine or chlorine, R²represents hydrogen or fluorine and R³ represents hydrogen.
 11. The Δ¹pyrroline of the Formula (I) according to claim 1, in which R²represents hydrogen or fluorine, where R² is in the 6-position of thephenyl ring to which it is attached.
 12. The Δ¹ pyrroline of the Formula(I) according to claim 1, in which X represents a direct bond and Yrepresents phenylene, preferably 1,4-phenylene.
 13. The Δ¹ pyrroline ofthe Formula (I) according to claim 9, in which X represents a directbond and Y represents phenylene, preferably 1,4-phenylene.
 14. A processfor preparing a compound of the Formula (I) according to claim 1,comprising A) treating an amino ketone of the Formula (II)

in which R¹, R², R³ and Het have the meanings given in claim 1 with aLewis acid or a protonic acid, optionally in the presence of a diluent,or B) reacting an azide of the Formula (III)

in which R¹, R², R³ and Het have the meanings given in claim 1 with atrialkylphosphine or a triarylphosphine or a trialkyl phosphite or areducing agent in the presence of a diluent and, optionally in thepresence of a catalyst, or C) reacting an amide of the Formula (IV)

in which R¹⁹ represents alkyl, halogenoalkyl, aryl or aralkyl and R¹,R², R³, Het have the meanings given in claim 1 with a N-deacetylatingagent, optionally in the presence of a diluent, or to obtain aΔ¹-pyrroline of the Formula (I-a)

in which Het¹ represents heteroaryl which is monosubstituted by R⁵⁻¹,R⁵⁻¹ represents the grouping —Y¹-E, Y¹ represents in each caseoptionally substituted phenylene or heterocyclylene and R¹, R², R³ and Ehave the meanings given in claim 1 D) reacting a Δ¹-pyrroline of theFormula (I-b)

in which Het² represents heteroaryl which is monosubstituted by R⁵⁻²,R⁵⁻² represents chlorine, bromine, iodine, —OSO₂CF₃ or —OSO₂(CF₂)₃CF₃,R¹, R² and R³ have the meanings given in claim 1 with a(hetero)cycle ofthe Formula (V)A¹-Y¹-E  (V) in which E has the meanings given in claim 1, Y¹ has themeanings given above, A¹ represents chlorine, bromine, iodine, —OSO₂CF₃or —OSO₂(CF₂)₃CF₃, in the presence of a catalyst, in the presence of adiboronic ester and, optionally in the presence of an acid binder and,optionally, in the presence of a diluent, in a tandem reaction, or E)reacting a Δ¹-pyrroline of the Formula (VI)

in which Het³ represents heteroaryl which is monosubstituted by A², A²represents -B(OH)₂, (4,4,5,5-tetramethyl-1,3,2-dioxaborolan)-2-yl,(5,5-dimethyl-1,3,2-dioxaborinan)-2-yl,(4,4,6-trimethyl-1,3,2-dioxaborinan)-2-yl or 1,3,2-benzodioxaborol-2-yland R¹, R² and R³ have the meanings given in claim 1 with a heterocycleof the Formula (V)A¹-Y¹-E  (V) in which E has the meanings given in claim 1, Y¹ and A¹have the meanings given above, in the presence of a catalyst, optionallyin the presence of an acid binder and optionally in the presence of adiluent, or F) reacting a Δ¹-pyrroline of the Formula (I-b)

in which R¹, R² and R³ have the meanings given in claim 1, Het² has themeanings given above with a boronic acid derivative of the Formula (VII)A²-Y¹-E  (VII) in which E has the meanings given in claim 1, Y¹ and A²have the meanings given above in the presence of a catalyst, optionallyin the presence of an acid binder and optionally in the presence of adiluent, or G) reacting a Δ¹-pyrroline of the Formula (I-c)

in which Het⁴ represents heteroaryl which is monosubstituted by R⁵⁻³,R⁵⁻³ represents bromine or iodine and R¹, R² and R³ have the meaningsgiven in claim 1 with an organometallic compound of the Formula (VIII)M-Y¹-E  (VIII) in which E has the meanings given in claim 1, Y¹ has themeanings given above, M represents ZnCl, Sn(Me)₃ or Sn(n-Bu)₃ in thepresence of a catalyst, optionally in the presence of an acid binder andoptionally in the presence of a diluent.
 15. A Δ¹ pyrroline of theFormula (I-d)

in which R¹, R², R³ and Het have the meanings given in claim
 1. 16. Anaminoketone of the Formula (II)

in which R¹, R², R³ and Het have the meanings given in claim
 1. 17. Anazide of the Formula (III)

in which R¹, R², R³ and Het have the meanings given in claim
 1. 18. Anamide of the Formula (IV)

in which R¹⁹ represents alkyl, halogenoalkyl, aryl or arylalkyl and R¹,R², R³ and Het have the meanings given in claim
 1. 19. A lactam of theFormula (IX)

in which Het has the meanings given in claim
 1. 20. A halide of theFormula (XV)

in which R¹, R², R³ and Het have the meanings given in claim 1 and Hal²represents halogen.
 21. A pesticide comprising one or more compounds ofthe Formula (I) according to claim 1 and one or more extenders and/orsurfactants.
 22. A method for controlling pests, comprising allowing acompound of the Formula (I) according to claim 1 to act on pests and/ortheir habitat.
 23. A process for preparing a pesticide comprising mixinga compound of the Formula (I) according to claim 1 with one or moreextenders and/or surfactants.